Geoscience Frontiers 14 (2023) 101624

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Research Paper

Tin transport and cassiterite precipitation from hydrothermal fluids

Xiangchong Liu a,b,c, Pingping Yu a, Changhao Xiao a,⇑
a
Institute of Geomechanics, Chinese Academy of Geological Sciences, Beijing 100081, China
b
Key Laboratory of Paleomagnetism and Tectonic Reconstruction, Ministry of Natural Resources, Beijing 100081, China
c
The Laboratory of Dynamic Diagenesis and Metallogenesis, Institute of Geomechanics, CAGS, Beijing 100081, China

a r t i c l e i n f o a b s t r a c t

Article history: Cassiterite (SnO2) is the main ore mineral of tin in magmatic–hydrothermal tin deposits, but tin transport
Received 8 November 2022 and precipitation mechanisms from hydrothermal fluids remain poorly understood. We critically evalu-
Revised 24 March 2023 ated aqueous tin speciation in hydrothermal fluids from extensive experimental data and thermody-
Accepted 22 April 2023
namic modeling. Sn(II) chloride complexes in hydrothermal fluids exist mainly as SnCl+, SnCl2(aq), and
Available online 27 April 2023
Handling Editor: Kristoffer Szilas
SnCl
3 . The revised Helgeson–Kirkham–Flowers model parameters of these three tin species and two
tin ions (Sn4+ and Sn2+) were derived from the correlation algorithms among these parameters, and
the standard molar properties of cassiterite were optimized to be internally consistent with the available
Keywords:
thermodynamic dataset. These thermodynamic parameters, together with the available equilibrium con-
Cassiterite stant equation of Sn(IV) chloride complexes, could reproduce the available solubility data of cassiterite in
Aqueous tin species acidic solutions at 400–700 °C under oxygen fugacity (f O2 ) levels buffered by hematite–magnetite (HM)
Precipitation mechanisms or nickel–nickel oxide (NNO). These comparisons allow modeling chemical systems of SnO2–NaCl–HCl–
Tin deposits H2O (liquid phase) to examine tin transport and cassiterite precipitation mechanisms under
Thermodynamic modeling tin-mineralizing conditions: 300–500 °C, 50–150 MPa, 2 molal NaCl, and f O2 levels from QFM
(quartz–fayalite–magnetite) to HM. Sn(II) chloride complexes are commonly interpreted to dominate
in aqueous tin speciation under f O2 = NNO, but our modeling results indicate that considerable contents
of Sn(IV) chloride complexes also exist in those reduced fluids with high HCl contents, consistent with
recent in situ high-temperature experiments and molecular dynamic simulations. The Sn(II)/Sn(IV) ratios
in fluids depends on f O2 , temperature, and HCl contents. A considerable amount of Sn(IV) possibly exist in
an early mineralization stage even under f O2 = NNO; if so, redox reactions are unnecessary to precipitate
cassiterite from these mineralizing fluids. We find that even if the f O2 levels are constant, simple cooling
can alter mineralizing fluids to be more oxidized (e.g., from QFM to HM) and cause cassiterite
precipitation, indicating that oxidizing agents are not necessary as previously thought. This explains
why cassiterite can precipitate in host rocks (e.g., sandstone or quartzite) that do not provide oxidizing
agents. A simple rise in f O2 levels and pH neutralization (e.g., greisenization) also cause cassiterite
precipitation. Cassiterite solubility in oxidized acidic hydrothermal fluids (NNO < f O2  HM) is high
enough to account for the tin contents of fluid inclusions from typical tin deposits, but the mineralization
potential of oxdized fluids is inferior to reduced fluids (f O2  NNO) under the same conditions.
Ó 2023 China University of Geosciences (Beijing) and Peking University. Published by Elsevier B.V. on
behalf of China University of Geosciences (Beijing). This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction evolved granites emplaced in the upper crust (Lehmann, 1990;

Tin (Sn) is considered a critical and strategic metal (Kamilli
et al., 2017). By far, the predominant ore mineral of tin is cassiterite
(SnO2), and cassiterite occurs in magmatic–hydrothermal deposits
and placer deposits, which account for approximately 20% and 80%
of the world’s tin resources, respectively (Kamilli et al., 2017).
These two types of tin deposits are genetically related to highly
⇑ Corresponding author.
E-mail addresses: xiaochanghao1986@126.com, xcliu@cags.ac.cn (C. Xiao).
Mao et al., 2019). Recent studies also identified the major roles
of metamorphic fluids in mobilizing tin from source rocks
(Romer et al., 2022).
Tin-associated granites are generally crystallized from reduced
(between quartz–fayalite–magnetite and nickel–nickel oxide buf-
fers) metaluminous to peraluminous granitic melts (Dubessy
et al., 1987; Mlynarczyk et al., 2003; Chen et al., 2013; Kinnaird
et al., 2016), in which Sn(II) dominates over Sn(IV) (e.g., Linnen
et al., 1995; Linnen et al., 1996; Bhalla et al., 2005; Farges et al.,
2006). Tin diffusivity in hydrous silicate melts was quantified by

https://doi.org/10.1016/j.gsf.2023.101624
1674-9871/Ó 2023 China University of Geosciences (Beijing) and Peking University. Published by Elsevier B.V. on behalf of China University of Geosciences (Beijing).
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
X. Liu, P. Yu and C. Xiao
Yang et al. (2016), and the partitioning of tin from granitic melts
into aqueous phase was re-examined by Zhao et al. (2022). Follow-
ing the dominance of Sn(II) at magmatic stage, extensive experi-
mental data under reduced hydrothermal conditions have been
derived for tin speciation and cassiterite solubility in the last sev-
eral decades (e.g., Kovalenko et al., 1986; Wilson and Eugster,
1990; Dorofeeva et al., 1994; Duc-Tin et al., 2007), and tin in min-
eralizing fluids is generally interpreted to be transported mainly as
Sn(II) chloride complexes (Jackson and Helgeson, 1985a, 1985b;
Heinrich, 1990; Halter et al., 1998). Thus, oxidation (H2 consump-
tion) is required for cassiterite precipitation in previous formation
models (cf. Heinrich, 1990; Lehmann, 2021):


þ 2H2 O ¼ SnO2 ðcassiteriteÞ þ 2Hþ þ xCl þ 0:5H2
2
x
SnClx
ð1Þ
However, the dominance of Sn(II) chloride complexes was
derived by regressing the solubility data after quenching. In con-
trast, recent in situ high-temperature experiments and molecular
dynamic simulations identified notable contents of Sn(IV) chloride
complexes in reduced solutions (Schmidt, 2018; Chou et al., 2021;
Wang et al., 2021), challenging the earlier view of the dominance
of Sn(II) in mineralizing fluids. Therefore, it is necessary to evaluate
the available experimental data in the literature and re-examined
tin speciation under hydrothermal conditions.
Reliable thermodynamic data of major aqueous tin species are
fundamental to modeling tin transport and cassiterite solubility
in hydrothermal fluids. The standard molar properties and revised
Helgeson–Kirkham–Flowers (HKF) model parameters of five aque-
ous tin species are derived in this study by evaluating extensive
experimental data and using the correlation algorithms among
these parameters for aqueous metal ions and complexes proposed
by Shock et al. (1997) and Sverjensky et al. (1997). The estimated
thermodynamic parameters of Sn(II) chloride complexes can
reproduce the available experimental solubility data. This paper
is organized as follows. First, the geochemical characteristics of
tin-mineralizing fluids are summarized to obtain the geochemical
characteristics and the tin contents in the mineralizing fluids. Sec-
ond, the methods used for estimating the thermodynamic proper-
ties of aqueous tin species and thermodynamic modeling are
described. Third, extensive experimental data of tin speciation
and cassiterite solubility under hydrothermal conditions are criti-
cally evaluated to derive major tin species in hydrothermal fluids.
Fourth, how tin is transported and the main variables affecting cas-
siterite solubility under tin-mineralizing conditions are analyzed
from modeling results.
2. Geochemical characteristics of tin-mineralizing fluids
Tin-mineralizing fluids belong to the NaCl–H2O ± CO2 systems
(Naumov et al., 2011). CO2-bearing fluid inclusions in gangue
minerals such as quartz and topaz are commonly found among
many magmatic-hydrothermal tin deposits (e.g., Mangas and
Arribas, 1987; Halter and Williams-Jones, 1995; Borges et al.,
2009; Jia et al., 2019) but occasionally in cassiterite (e.g.,
Linnen, 1998; Schmidt et al., 2021). These aqueous–carbonic
inclusions were interpreted to have a magmatic or metamorphic
origin (e.g., Linnen, 1998; Dewaele et al., 2010; Van Daele et al.,
2018).
The dataset of Naumov et al. (2011), which includes 320 Sn and
Sn–W deposits, suggests that most fluid inclusions in cassiterite
have homogenization temperatures ranging from 300 to 500 °C.
This temperature range is consistent with earlier compiled data-
sets (e.g., Lehmann, 1990) and numerous later studies (e.g.,
Korges et al., 2017; Myint et al., 2018; Jia et al., 2019; Liu et al.,
2020a; Han et al., 2023). Tin-mineralizing fluids generally have
2
Geoscience Frontiers 14 (2023) 101624
salinities <10 wt.% NaCl equivalent (Naumov et al., 2011), but the
fluid salinities at earlier stages may reach higher levels (e.g.,
Myint et al., 2018; Korges et al., 2020). The mineralization pres-
sures of most fluid inclusion data lie in the range of 50–150 MPa
(Naumov et al., 2011).
Tin-mineralizing fluids are generally acidic and leave typical
mineral assemblages of quartz–muscovite–fluorite–topaz (grei-
sens) after flowing through granitic rocks (Štemprok, 1987;
Pirajno, 1992; Meinert et al., 2005). Constraints from common
mineral assemblages and the mineral–solution equilibrium in tin
deposits suggest that the mineralizing fluids have pH levels of 4–
6 (Patterson et al., 1981; Jackson and Helgeson, 1985b; Polya,
1989). At their sources, the mineralizing fluids may be more acidic
than those aforementioned pH levels. Values of oxygen fugacity
(see Fig. 1) are estimated from gas compositions (CO2 and CH4)
of fluid inclusions and from mineral equilibrium and mostly lie
between those of the mineral assemblages of quartz–fayalite–mag
netite (QFM) and nickel–nickel oxide (NNO) buffers (Patterson
et al., 1981; Jackson and Helgeson, 1985b; Polya, 1989; Xiang
et al., 2018; Schmidt et al., 2021).
Published in situ compositions of fluid inclusions from Sn–W
and W–Sn deposits were compiled in this study to show the distri-
bution of tin contents in mineralizing fluids and place a quantita-
tive constraint on subsequent thermodynamic modeling. These
content data come from typical tin deposits of four world-class
tin provinces, including the Sn–W deposits around the Mole Gran-
ite, Australia (Audétat et al., 2000); the Sn–W deposits in the Erzge-
birge, Germany and the Czech Republic (Korges et al., 2017); the
Huanuni tin deposit, Bolivia (Müller et al., 2001); and the Piaotang
and Maoping W–Sn deposits in the Nanling Range, China (Legros
et al., 2019). The boxplot in Fig. 2 shows that the tin contents of
mineralizing fluids range from a few to 104 parts per million
(ppm), with an average of 529 ppm. Tin contents between 10
and 1000 ppm account for 83% of the total data, so this range of
tin concentrations can be used to place a lower limit on cassiterite
solubility in hydrothermal fluids under tin-mineralizing
conditions.
3. Methods
Chemical mass transfer modeling has been used to decipher
tin transport and cassiterite deposition from mineralizing fluids
(Jackson and Helgeson, 1985a, 1985b; Heinrich, 1990; Tornos,
1997; Halter et al., 1998). Heinrich (1990) evaluated several
key chemical and physical parameters that may cause cassi-
terite precipitation using fluid-buffered and rock-buffered mass
transfer modeling, in which the thermodynamic data of Sn(II)
chloride complexes came from Pabalan (1986). As shown later,
the high contents of SnCl2
4 interpreted by Pabalan (1986) in
their experiments is problematic. Halter et al. (1998) modeled
fluid–rock interactions during greisenization in a tin deposit
using the equilibrium constants of SnCl+ fitted by Wilson and
Eugster (1990). The chemical systems of cassitierite in
hydrothermal fluids were modeled and the concentrations of
aqueous tin species and the solubility of cassiterite were calcu-
lated by the method of equilibrium constants. This method
assumes that a chemical system is at equilibrium and that all
species in the chemical system are stable. The concentrations
and activities of all species can be derived by solving nonlinear
equations.
Each chemical reaction in the chemical system at equilibrium
produces a nonlinear equation. For example, the nonlinear equa-
tion for the association of Na+ and Cl
into NaCl(aq) is:
cNaClðaqÞ mNaClðaqÞ
K¼ ð2Þ
cNaþ mNaþ cCl
mCl

X. Liu, P. Yu and C. Xiao Geoscience Frontiers 14 (2023) 101624

Fig. 1. The oxygen fugacity of tin-mineralizing fluids available in the literature. The curves of mineral–buffered oxygen fugacity were calculated at a fixed pressure of
200 MPa using thermodynamic data from Helgeson (1978), Robie et al. (1978), and Berman (1988). The points come from Jackson and Helgeson (1985b) (the tin deposits from
the Southeast Asian tin belt), Patterson et al. (1981) (the Renison Bell tin deposit, Australia), Polya (1989) (the Panasqueira tungsten-tin deposit, Portugal), and Xiang et al.
(2018) (the Jiumao tin deposits, China). The data of Schmidt et al. (2021) were calculated at a fixed pressure of 50 MPa based on average compositions of primary fluid
inclusions in cassiterite from seventeen tin deposits in the world. HM, hematite-magnetite buffer; NNO, nickel-nickel oxide buffer; QFM, quartz-fayalite-magnetite buffer;
FM, ferrous oxide-magnetite; FI, ferrous oxide-iron.

Fig. 2. The in situ Sn contents of fluid inclusions from typical Sn–W and W–Sn deposits. The tin contents (unit in ppm) have been logarithmically transformed with respect to
base 10. On each box, the central mark indicates the median, and the bottom and top edges of the box indicate the 25th and 75th percentiles, respectively. N represents the
sampling number of each dataset. The average of the 325 data is 529 ppm.

in which K is the equilibrium constant; and mNaClðaqÞ and cNaClðaqÞ are solutions, respectively. The activity coefficients of electrically
the concentration and the activity coefficient of NaCl(aq) in aqueous charged species in the models were calculated by an extended

3
X. Liu, P. Yu and C. Xiao
Debye–Hückel equation (Helgeson et al., 1981), and those of neutral
species were derived from the Setchénow equation (see Eq. (3) in
Miron et al., 2016). The activity of H2O is generally assumed to be
unity at room temperature in geochemical modelling (Anderson,
2005). However, the high-temperature experimental data of
Aranovich and Newton (1996) suggest that the activity of H2O
approximately equal its mole fraction at 620–640 °C and 200 MPa
in concentrated NaCl solutions, and H2O activity rapidly decreases
below the mole fraction with increasing pressure. The tin-
mineralizing conditions and most experimental data in the litera-
ture do not exceed the temperature and pressure conditions of
Aranovich and Newton (1996), so H2O activity in this study was
assumed to equal its mole fraction in solutions. These equations
of activity coefficients were calculated using the R language free
package CHNOSZ (Dick, 2019). CHNOSZ is an open–source R lan-
guage package that uses the revised HKF electrostatic equations of
state (Helgeson et al., 1981) and the thermodynamic data of miner-
als and aqueous species in SUPCRT (Johnson et al., 1992). Charge
and mass balance relations are also required to calculate the con-
centrations of the species in the models. The nonlinear equations
were solved using another free package in R language, rootSolve
(cf. Soetaert and Herman, 2008), and the solving process was similar
to that presented in the appendix of our previous paper (Liu and
Xiao, 2020). The concentration of a species is expressed as molal
(mol kg
1 H2O) throughout this article.
The revised HKF electrostatic equations of state (Helgeson et al.,
1981; Tanger and Helgeson, 1988) is the most accepted model in
geochemical applications and is conventionally restricted to
1000 °C and 500 MPa at liquid-like fluid densities (>0.35 g cm
3)
(Shock et al., 1997; Dolejš, 2013). Most thermodynamic data of
minerals and aqueous species (e.g., H+, OH
, and Cl
) used in the
models come from the SUPCRT database (Johnson et al., 1992).
The HKF model parameters of Na+, NaCl(aq), and NaOH(aq)
updated by Miron et al. (2016) were used, and those of cassiterite
were updated in the present study. The standard molar properties
and revised HKF model parameters of five aqueous tin species
(Sn4+, Sn2+, SnCl+, SnCl2(aq), and SnCl

3 ) were calculated from the
correlation algorithms proposed by Shock et al. (1997) and
Sverjensky et al. (1997). The Akinfiev-Diamond model was used
for aqueous nonelectrolytes such as O2(g) and H2(g) (Akinfiev
and Diamond, 2003).
4. The thermodynamic properties of cassiterite
To our knowledge, at least three datasets for the thermody-
namic properties of cassiterite are available in the literature (see
Table 1). The thermodynamic parameters of cassiterite in the
SUPCRT database come from Robie et al. (1978). Later, these data
were updated by Robie and Hemingway (1995) from the experi-
mental data of Zhogin et al. (1980) and Bannister (1986) and the
dataset reported by CODATA (Cox et al., 1989). Gamsjäger et al.
(2012) also calculated the standard molar properties of cassiterite
Table 1
The available standard molar properties of cassiterite in the literature.
Sources Df GoPr ;T r SoPr ;T r
(kJ mol
1) (J mol
1)
SUPCRT1
519.90 ± 0.75 52.30 ± 1.25
Robie and Hemingway (1995)
515.8 ± 0.2 49.0 ± 0.2
Gamsjäger et al. (2012)
516.64 ± 0.21 51.77 ± 0.14
Gurevich et al. (2004) – 51.82 ± 0.07
This study
514.62 ± 2.83 51.82
P r = 0.1 MPa, T r = 298.15 K.
1
, data from Robie et al. (1978).
Geoscience Frontiers 14 (2023) 101624
from previous experimental data. Despite these available datasets
of cassiterite, its thermodynamic properties were updated for the
following two reasons. The first and most important reason is that
each dataset comes from several sources and no one has tested its
consistency with the available internally consistent thermody-
namic dataset of minerals and gas species (Holland and Powell,
2011). The second reason is that the standard molar entropy and
heat capacity measured by Gurevich et al. (2004), whose experi-
mental data are more reliable than those of Zhogin et al. (1980)
(see Gamsjäger et al., 2012, pp. 128–133), are 5.8% and 3.8% higher
than the corresponding values recommended by Robie and
Hemingway (1995) (see Table 1).
To make the thermodynamic properties of cassiterite consistent
with the dataset of Holland and Powell (2011), we first updated the
heat capacity function from the available experimental data. Then,
we optimized the standard molar Gibbs energy of cassiterite from
the available thermodynamic equilibrium data that are associated
with cassiterite, gas species (e.g., O2(g) and H2(g)), and other oxides
(e.g., Cu2O and NiO).
Kapustinskii et al. (1936) reported the most reliable high-
temperature heat capacity of cassiterite until now, and their data
were used to fit the heat capacity equation by Robie et al. (1978)
and Robie and Hemingway (1995). Their high-temperature data,
together with the low-temperature heat capacity data of
Gurevich et al. (2004), were employed to fit the Hass–Fisher heat
capacity function against temperature (Haas and Fisher, 1976):
C oP ¼ a þ bT þ cT
2 þ dT
0:5 þ eT 2 ð3Þ
Fig. 3 shows that the fitted coefficients reproduce the experi-
mental data with an absolute error no >0.6 J mol
1 K
1. To be con-
sistent with the heat capacity data of Gurevich et al. (2004), the
standard molar entropy of 51.82 J mol
1 was used in this study.
For a solid phase, its molar Gibbs free energy of formation Df G0PT
can be calculated from the equation
Z Z
T T
C 0P
Df G0PT ¼ Df G0T r ;Pr
ðT
T r ÞS0T r ;Pr þ C 0P dT
T dT
Tr Tr T

0
þ V T r ;Pr ðP
Pr Þ ð4Þ
in which T r = 298.15 K; P r = 0.1 MPa; and Df GoT r ;Pr is the standard
molar Gibbs free energy of formation, the standard molar entropy
SoT r ;Pr , the heat capacity C op , and the standard molar volume V oT r ;Pr .
The Df G0T r ;Pr values of cassiterite were calculated from the ther-
modynamic equilibrium data of the following chemical systems:
Sn–O (Bannister, 1986; Li-Zi et al., 1994; Mallika et al., 2001),
Sn–Cu–O (Schaefer, 1984), Sn–H–O (Atarashiya et al., 1960), and
Sn–Ni–O (Belford and Alcock, 1965; Petot-Ervas et al., 1975). These
experimental studies reported the molar Gibbs energy changes of
the chemical reactions shown in Table 2; thus, the Df G0T r ;Pr of cassi-
terite is the only variable for each experimental point (see Eq. (4)).
The thermodynamic data of cuprite (Cu2O) and bunsenite (NiO) in
Holland and Powell (2011) were used. A total of 138 experimental
points produce an average Df GoT r ;Pr ¼
514.62 kJ mol
1 of cassi-
terite (Fig. 4), slightly greater than those of Robie and
Hemingway (1995) (
515.8 kJ mol
1) and Gamsjäger et al.
C op
(2012) (
516.64 kJ mol
1). Note that the standard deviation of this
(J mol
1 K
1)
study is significantly larger than those reported in the other two
52.59 studies. Such a large standard deviation is possibly caused by mult-
53.22
55.26 ± 0.09 ple sources of experimental erros. For example, the Df G0T r ;Pr values
55.24 ± 0.03 of cassiterite derived from the data of Bannister (1986) at <700 °C
55.24 deviate from the average value by up to 7 kJ mol
1, while those
over 700 °C are mostly within 1–2 kJ mol
1. Overall, the updated
thermodynamic properties of cassiterite are internally consistent
4
X. Liu, P. Yu and C. Xiao Geoscience Frontiers 14 (2023) 101624

Fig. 3. The heat capacity of cassiterite fitted from the available experimental data. (a) The empirical equation fitted by this study matches the low-temperature and high-
temperature experimental data, while the values reproduced from the equation of Robie and Hemingway (1995) are significantly lower than the low-temperature
experimental data. The heat capacities of Robie and Hemingway (1995) under hydrothermal conditions are close to the empirical equation fitted by this study because both
two equations employed the high-temperature data of Kapustinskii et al. (1936). Two samples were used by Gurevich et al. (2004), Russian pure tin (IV) oxide (RP) and
commercial tin (IV) oxide product of Alfa Aesar (AA). (b) The absolute residuals of the fitted heat capacity do not exceed 0.6 J mol
1 K
1.

Table 2 with those of cuprite (Cu2O) and bunsenite (NiO) in Holland and
The chemical reactions for optimizing the Df GoPr ;T r value of cassiterite. Powell (2011).
Numbers Chemical reactions References
1 Sn(l) + O2(g) = SnO2(s) 1, 2, 3 5. Tin species and chemical reactions under hydrothermal
2 Sn(s) + 2Cu2O = SnO2(s) + 4Cu 4 conditions
3 Sn(l) + 2H2O = SnO2(s) + 2H2(g) 5
4 Sn(s) + 2NiO = SnO2(s) + 2Ni 6, 7
Tin species in hydrothermal fluids exist mainly as tin chloride
References: 1, Bannister (1986); 2, Li-Zi et al. (1994); 3, Mallika et al. (2001); 4, and fluoride complexes (Wilson and Eugster, 1990; Taylor and
Schaefer (1984); 5, Atarashiya et al. (1960); 6, Belford and Alcock (1965); 7, Petot-
Wall, 1993; Sherman et al., 2000; Müller and Seward, 2001; Duc-
Ervas et al. (1975).
Tin et al., 2007). Although water vapor can carry an appreciable

Fig. 4. The optimized Df G0T r ;Pr value of cassiterite from the available equilibrium data. A total of 138 experimental data points give an average of Df G0T r ;Pr =
514.62 KJ mol
1
with a standard deviation of 2.83 KJ mol
1. The shaded area (
514.62 ± 5.66 kJ mol
1) covers most of the experimental determinations.

5
X. Liu, P. Yu and C. Xiao
amount of tin (Migdisov and Williams-Jones, 2005), the typical tin-
mineralizing conditions (see Section 2) indicate that the aqueous
liquid phase plays the main role in ore forming processes. There-
fore, we focused on the thermodynamic properties of aqueous Sn
(II) and Sn(IV) ions, hydroxides, and chloride complexes. Tin fluo-
ride complexes are not considered in this study.
There are several reviews about inorganic Sn(II) and Sn(IV) spe-
cies from extensive experimental data available in the literature
(Lothenbach et al., 1999; Séby et al., 2001; Cigala et al., 2012;
Gamsjäger et al., 2012). Séby et al. (2001) published a review of
Sn(II) hydrolytic and complex species at room temperature from
the literature. Later, Cigala et al. (2012) critically reviewed Sn(II)
species with the most important natural inorganic ligands (OH
,
Cl
, F
, CO2
2
3

3 , SO4 , and PO4 ) and derived their formation con-
stants and the formation enthalpy changes at 25 °C. Gamsjäger
et al. (2012) also evaluated aqueous tin species in solutions mostly
at room temperature. These previous reviews provide a basis for
interpreting aqueous tin species in hydrothermal fluids at temper-
atures over 300 °C.
We evaluated the available experimental data (Table 3) and
estimated the thermodynamic parameters of five aqueous tin spe-
cies (Table 4) from the correlation algorithms shown in Supple-
mentary Data 1. All the cited experimental solubility data are
listed in Supplementary Data 2. Here, we follow the convention
adopted by Wagman et al. (1982) and Shock et al. (1997) that
H2O is subtracted from the stoichiometry of some aqueous species
(e.g., hydroxide complexes). For example, the uncharged Sn(II)
hydroxide Sn(OH)2(aq) is replaced by SnO(aq), and Sn(OH)4(aq) is
replaced by SnO2(aq). The reason for this simplicity is because
the formulas with or without the number of molecules of water
are generally thermodynamically equivalent (cf, Wagman et al.,
1982, pp. 2–22). This pragmatic decision ignores the molecular
structure of aqueous species studied. Note that no one has tested
whether the hydroxides and chloride complexes of Sn(II) and Sn
(IV) with a few number of water molecules are thermodynamically
equivalent to those without water molecules. The following abbre-
viations of mineral assemblage–buffered f O2 levels are used for
simplicity: NNO, nickel–nickel oxide; MM, MnO2–Mn2O3; HM,
hematite–magnetite; PPM: pyrite–pyrrhotite–magnetite.
5.1. The f O2 boundary between the Sn(II) and Sn(IV) dominance fields
Tin in hydrothermal fluids has two oxidation states, +2 and +4.
The dominant tin species in solutions under f O2  NNO is com-
monly interpreted to be stannous (e.g., Kovalenko et al., 1986;
Kovalenko et al., 1989; Wilson and Eugster, 1990; Kovalenko
et al., 1992; Taylor and Wall, 1993; Dorofeeva et al., 1994; Duc-
Tin et al., 2007). However, this interpretation is derived by regress-
ing the solubility data after quenching and is challenged by recent
in situ experiments. Schmidt (2018) proposed from his in situ
Raman spectroscopic data that the f O2 boundary between Sn(II)
and Sn(IV) dominance fields lies between f O2 ¼ HM and a few log
units below f O2 ¼ NNO. Later, Schmidt et al. (2021) constrained
the boundary to be between f O2 near NNO and the rhenium-
rhenium oxide buffered f O2 levels (close to HM), and Chou et al.
(2021) identified the in situ Raman spectra of Sn(IV) chloride com-
plexes in solutions at 300 °C and f O2 ¼ NNO (see their Fig. 3a).
These recent experimental data suggest that the amount of aque-
ous Sn(IV) species in those solubility experiments under
f O2 ¼ NNO cannot be neglected.
The tin species in solutions under f O2  HM is generally inter-
preted to be stannic (Wilson and Eugster, 1990). The experiments
under unconstrained oxygen fugacities should be at higher f O2
levels, and the predominant aqueous tin species was also stannic
6
Geoscience Frontiers 14 (2023) 101624
(e.g., Klintsova and Barsukov, 1973; Dadze et al., 1981; Sorokin
and Dadze, 1994; Sherman et al., 2000; Liu et al., 2020b). For sim-
plicity, only aqueous Sn(IV) species were used to analyze the
experimental data under unconstrained f O2 , and both Sn(IV) and
Sn(II) species were considered to interpret the experimental data
if the f O2 values were known.
5.2. Sn4+
The oxidation state of tin in cassiterite is stannic (Sn4+). The
available standard molar Gibbs free energies of formation Df GoT r ;Pr
of Sn4+ are highly controversial. Wagman et al. (1968) calculated
the Df GoT r ;Pr of Sn4+ to be 2.51 kJ mol
1, which was recommended
by National Bureau of Standards/National Institute of Standards
and Technology (NBS/NIST) (Wagman et al., 1982; Reed, 2020).
This value was also used by Jackson and Helgeson (1985a) to pre-
dict the molar Gibbs free energies of formation of Sn4+ under
hydrothermal conditions. In contrast, the Df GoT r ;Pr =
19.318 kJ mol
1
derived by Ryzhenko et al. (1997) is much lower than that of
Wagman et al. (1968). Note that the procedure by which
Ryzhenko et al. (1997) derived this value is unknown. Gamsjäger
et al. (2012) derived a much higher Df GoT r ;Pr ¼ 46:7  3:9 kJ mol
1
from the standard electrode potential of the Sn4+/Sn2+ redox couple
in Gajda et al. (2009). Rai et al. (2011) derived logK =
64.39 ±
0.32 of the following chemical reaction from their experimental
data at 23 ± 2 °C and 1 bar:
SnO2 ðsÞ þ 2H2 O ¼ Sn4þ þ 4OH
ð5Þ
However, this logK value is possibly problematic. First, Rai et al.
(2011) neglected the formation of Sn(IV) chloride complexes in
0.0003–1.0 molal HCl solutions, whereas the experimental data
of Gajda et al. (2009) suggest the dominance of Sn(IV) chloride
complexes at >3  10
5 molal Cl. Second, Sn4+ is a minor species
in the solutions of Rai et al. (2011) and calculating the logK of Reac-
tion (5) is easily affected by ignoring Sn(IV) chloride complexes.
Therefore, the logK of Reaction (5) derived by Rai et al. (2011) can-
not be used to test the above Df GoT r ;Pr values of Sn4+. As a result, a
recommended Df GoT r ;Pr value of Sn4+ is not generated here. From
later calculations, even if a lower Df GoT r ;Pr value of Sn4+ is used, its
concentrations in solutions are extremely low and can be ignored
for geologic fluids.
The standard molar entropy SoT r ;Pr of Sn4+ in the dataset compiled
by Wagman et al. (1968) is
117.15 J mol
1 K
1, but the source is
unknown. Sassani and Shock (1992) derived a value of SoT r ;Pr =
472.
37 J mol
1 K
1 from their correlations between the SoT r ;Pr of aqueous
ions and their effective electrostatic radii, which is close to the one
predicted by Gamsjäger et al. (2012) using the modified Powell–
Latimer correlation (
468 ± 33 J mol
1 K
1). To maintain consis-
tency with the revised HKF model parameters of other aqueous
tin species, SoT r ;Pr =
472.37 J mol
1 K
1 derived by Sassani and
Shock (1992) was used in this study. The standard heat capacity
C op , the standard molar volume V oT r ;Pr , and the revisd HKF model
parameters of Sn4+ were derived using the correlation algorithms
in Supplementary Data 1.
5.3. Sn2+
The structure of hydrated Sn(II) ions in aqueous solutions was
recently identified by Persson et al. (2016). We found that the C op
of Sn2+ in the SUPCRT database was not the value calculated from
Eq. (18) of Shock et al. (1997) (see Eqs. A1–A2 in Supplementary
Data 1) and the SoT r ;Pr recommended by Cox et al. (1989), and this
incorrect value leads to incorrect estimates of its revised HKF
X. Liu, P. Yu and C. Xiao Geoscience Frontiers 14 (2023) 101624

Table 3
Summary of hydrothermal experiments for cassiterite solubility or tin speciation.

Authors Methods T (°C) P (MPa) Aqueous solution f O2 Dominant tin species

Kovalenko et al. Solubility 500 100 NaOH (0.0001–0.5 molal) NNO Sn(OH)2

4
(1992)
Kovalenko et al. Solubility 500 100 NaOH (0.18–0.5 molal)–NaCl NNO Sn(OH)2Cl

(1992) (0.5–4 molal)
Chen (1986) Solubility 300–450 0.1–45 HCl (0.001–0.1 molal) charcoal* Sn(II)-Cl complexes
Kovalenko et al. Solubility 500–700 100 HCl–NaCl–KCl NNO SnCl2(aq), SnOHCl (netural pH)
(1986)
Pabalan (1986) Solubility 200–350 Psat HCl (?) IM SnCl2
n
n (1  n  4)
Li (1988) Solubility 200–500 100 HCl NNO SnCl2(aq), SnOHCl
+
Wilson and Solubility 400–600 150 HCl (0.2–4.45 molal) NNO SnCl , SnCl2(aq)
Eugster (1990)
Taylor and Wall Solubility 700–800 200 HCl + NaCl + KCl [QFM
0.7, SnCl2(aq), SnOHCl, alkali-chloride
(1993) QFM + 1.5] complexes (e.g. KSnOHCI2)
Sherman et al. EXAFS spectra 25–350 0.1 SnCl2–HCl (0.5–2.5 molal) unknown** SnCl2

4
(2000)
Müller and Seward spectrophotometry 25–300 Psat HCl (0.01 molal)–NaCl (0.01– Ar* SnCl2
n
n (1  n  4)
(2001) 2.936 molal)
Duc-Tin et al. Synthetic fluid 700 140 HCl (0.5–4.4 molal)–NaCl (5– NNO SnCl2(aq), Sn(OH)Cl
(2007) inclusions 35 wt.%)
Duc-Tin et al. Synthetic fluid 700 140 NaCl (5–35 wt.%) NNO Sn(OH)Cl
(2007) inclusions
Wang et al. (2021) Molecular 57–700 0.1–150 SnCl2
n
n (n = 0–4) unknown** SnCl

3 (<300 °C), SnCl2(aq) (500–700
dynamics °C)
simulation
Klintsova and Solubility 25–200 0.1 Water unknown** SnO2(aq)
Barsukov
(1973)
Dadze et al. (1981) Solubility 200–400 101.3 Water unknown** SnO2(aq)
Liu and Chen Barnes volumetry 25–350 0.1–60 Water, NaCl (0.01–1 molal) unknown** SnO2(aq)
(1986)
Sorokin and Dadze Solubility 200–400 1.6–150 water unknown** SnO2(aq)
(1994)
Klintsova and Solubility 25–200 0.1 NaOH unknown** Sn(OH)
2

5 ,Sn(OH)6
Barsukov
(1973)
Liu and Xiao Raman 400–850 300–850 Li2CO3, Na2CO3 unknown** Sn(OH)2

6
(2020) spectroscopy
Klintsova et al. Solubility 25–200 0.1 HNO3 + NaF unknown** SnO2(aq)
(1975)
Dadze et al. (1981) Solubility 200–400 101.3 HCl (0.0025–0.04 molal) unknown** SnO2(aq), Sn(OH)+3
Dadze et al. (1981) Solubility 200–400 101.3 HNO3 (0.01–0.5 molal) unknown** SnO2(aq)
Kovalenko et al. Solubility 500 100 HCl–NaCl–KCl MM SnOHCl03, SnO2(aq)
(1986)
Li, 1988) Solubility 200–500 100 HCl (0.01–1.0 molal) unknown** SnO2(aq), Sn(OH)3Cl0
Wilson and Solubility 500–600 150 HCl (0.174–4.64 molal) HM SnCl+3
Eugster, 1990
Sorokin and Dadze Solubility 200–400 101.3 HCl (0.001–0.5 unknown** SnO2(aq), Sn(OH)+3, Sn(OH)3Cl
(1994) molal) ± HNO3 ± KCl

Sherman et al. EXAFS spectra 25–350 0.1 SnCl4 (0.01 molal) + HCl (0.11 unknown** SnCl2

6
(2000) molal) + NaCl (2 molal)
Chou et al. (2021) Raman 30 Psat 0.5 molal SnCl4 + 0.5 molal HCl unknown** SnCl
0 +
5 , SnCl4(aq), SnCl3
spectroscopy
Kokh et al. (2016) hydrothermal 349–351 13.9–23.2 CO2–NaCl–KCl HM SnCl4(aq)
reactor
Kokh et al. (2017) hydrothermal 450 57–68 CO2–KCl PPM SnO2(aq)
reactor
Schmidt (2018) Raman 500–600 194–1330 HCl (1.63–4.26 molal) Ar ± H2 ± CH4* SnCl4(aq), SnCl+3, SnCl

5
spectroscopy

The oxygen fugacity f O2 : IM, iron–magnetite; NNO, nickel-nickel oxide; MM, MnO2–Mn2O3; HM, hematite–magnetite; PPM: pyrite–pyrrhotite–magnetite. EXAFS, extended
X-ray absorption fine structure. One asterisk (*) above unknown f O2 represents that the oxygen fugacity was controlled by the material before the asterisk, but the precise f O2
is unknown; two asterisks (**) above unknown f O2 represent that the oxygen fugacity was unconstrained. Under the mineral assemblage of MnO2–Mn2O3 at 500 °C and
100 MPa, logf O2 ¼ –0.22 bar (1 bar = 0.1 MPa).

model parameters (see Eqs. A10–A11 in Supplementary Data 1).
The C op and revised HKF model parameters of Sn2+ were recalcu-
lated from the corresponding correlation algorithms. Fig. 5 shows
that the calculated molar Gibbs free energy of formation of Sn2+
at 100–500 °C and 100 MPa differs from those by Shock et al.
(1997) by no more than 3.3 kJ mol
1.
5.4. Sn(II) hydroxide complexes
Sn(II) has a strong tendency to hydrolyze and forms several
aqueous hydroxide complexes at room temperature (Cigala et al.,
2012; Gamsjäger et al., 2012). At low tin levels (<0.02 molal =
2374 ppm), Pettine et al. (1981) identified only three mononuclear

7
X. Liu, P. Yu and C. Xiao Geoscience Frontiers 14 (2023) 101624

Table 4
The standard state properties and revised HKF model parameters of aqueous tin species and Th4+.

Species Df GoPr ;T r (cal HoPr ;T r (cal K
1 SoPr ;T r (cal K
1 C op (cal K V oPr ;T r (cm3 a1*10 a2*10
2 a3 a4*10
4 c1 c2*10
4 xPr ;T r *10
5
mol
1) mol
1) mol
1) mol
1) mol
1) (cal K
1 (cal (cal*K mol
1 (cal*K (cal K
1 (cal*K (cal mol
1)
mol
1) mol
1) bar
1) mol
1) mol
1) mol
1)
Sn4+ 600a
18,083.8x
112.9b
56.12x
61.76x
5.3731x
20.9004x 13.9648x
1.915x 9.0585x
14.4665x 3.884x
Th4+
168,500
101c
183,800
53.54d
60.6d
5.2739x
20.6582x 13.8696x
1.9250x 8.9637x
13.9401x 3.7093x
Sn2+
6570
2249.42
3.99
11.14x
15.5584 0.0142
7.7466 8.7948
2.4588 9.9465x
5.3042x 1.1190
SnCl+
39,962b
41,670x 17.5442x 8.7913x 9.2717x 3.1277x
0.1446 x 5.8069x
2.7730x 13.8796 x
1.2438x 0.278x
SnCl2(aq)
72,232b
81,852x 32.2825x 13.9082x 37.0637x 6.8239 x 8.8804x 2.2598x
3.1461x 13.9676x
0.2015x
0.038x
SnCl
3
103,547b
121,668x 45.0481 x 4.2091x 68.0292x 11.3814 x 20.0081x
2.1139x
3.6061x 17.0106x
2.1772x 0.9093x

The data with a superscript come from the following references: a, Wagman et al. (1968); b, Sassani and Shock (1992); c, Morss and McCue (1976); d, Hovey (1997); x, this
study. Those parameters without a superscript are from Shock et al. (1997). Using calorie in the above parameters is a tradition in the thermodynamic database SUPCRT.
1 cal = 4.184 J. P r = 0.1 MPa, T r = 298.15 K.

Fig. 5. The molar Gibbs free energy of formation of Sn2+ calculated by the HKF parameters given by Shock et al. (1997) and those updated by this study. The Gibbs free
energies of formation calculated by the updated parameters are smaller than those by Shock et al. (1997) and their difference increases with temperature.

complexes SnOH+, SnO(aq), and HSnO
2 at 20 °C and pH = 2–11.
From potentiometric titrations, Raman, Mössbauer and X-ray
absorption spectroscopic data, Bajnóczi et al. (2014) found that
Sn(OH)


3 (here replaced by its dehydrated form HSnO2 ) was the
predominant Sn(II) species in hyper-alkaline (pH > 13) aqueous
solutions at room temperature. The local structure of tin in their
experiments was independent of the NaOH (2–12 molal) and Sn
(II) (0.05–0.2 molal) contents. Therefore, it is safe to ignore SnO2

2 5.5. Sn(IV) hydroxide complexes
and polynuclear complexes (e.g., Sn2(OH)2+ 2 ) even in hyperalkaline
solutions at room temperature.
The experimental data of Sn(II) hydrolytic species under
hydrothermal conditions are extremely limited (Kovalenko et al.,
1992). Kovalenko et al. (1992) measured cassiterite solubility in
NaOH solutions (0.001–0.5 molal) at 500 °C, 100 MPa, f O2 ¼ NNO.
They speculated the dominance of SnO2
2 to explain the high con-
centrations of tin in alkaline solutions, but significant contents of
this species are inconsistent with recent findings in alkaline
8
solutions at 25 °C (e.g., Bajnóczi et al., 2014). To our knowledge,
the data of Kovalenko et al. (1992) are the only solubility data of
cassiterite in alkaline solutions under reducing hydrothermal con-
ditions. Therefore, more hydrothermal solubility experiments
should be conducted to confirm or reject the high contents of
high-order Sn(II) hydrolytic species.
5.5.1. The dominance of SnO2(aq) in weakly pH–acidic and neutral
solutions
Sn(IV) also tends to be hydrolyzed in solutions and the available
experimental data of Sn(IV) hydrolytic species at room tempera-
ture are consistent (Hummel et al., 2002; Gamsjäger et al., 2012).
From the independent relationship between tin concentrations
and pH = 1.9–8 at 25 °C, the uncharged hydrolytic species SnO2(aq)
was interpreted to be the predominant aqueous Sn(IV) species
X. Liu, P. Yu and C. Xiao
(Amaya et al., 1997; Gamsjäger et al., 2012). As pH increases to
alkaline levels, tin concentrations in solutions significantly
increase and HSnO
3 and SnO3
2

were interpreted to exceed
SnO2(aq) (Amaya et al., 1997). Rai et al. (2011) derived similar
results from their solubility experiments at 23 ± 2 °C.
The influence of pH on the dominant Sn(IV) hydroxide com-
plexes extends to hydrothermal conditions. SnO2(aq) was inter-
preted by earlier experimental studies to be the dominant Sn(IV)
species in water at 200–400 °C (Dadze et al., 1981; Liu and Chen,
1986; Sorokin and Dadze, 1994) and in weakly acidic solutions at
200–450 °C (Dadze et al., 1981; Sorokin and Dadze, 1994). This is
similar to the dominance of the neutral hydrolytic species GeO2(-
aq) of germanium (another element in Group 14 of the periodic
table) in water and acidic solutions (Pokrovski and Schott, 1998;
Pokrovski et al., 2005). From the absence of a positive correlation
between tin concentrations and Cl concentrations in their experi-
ments at 350–450 °C, Kokh et al. (2017) also raised the possibility
that SnO2(aq) was the dominant tin species in low-concentration
CO2 and CO2-free solutions. In alkaline solutions, Klintsova and
Barsukov (1973) employed SnO2
3 and SnO2(aq) to interpret their
solubility data at 200 °C. Recently, Liu et al. (2020b) identified
the Raman spectrum of SnO2
3 in SnO2–NaOH–H2O experiments
conducted in a hydrothermal diamond-anvil cell. The above analy-
sis suggests that SnO2(aq) is the main Sn(IV) hydrolytic species in
pH neutral and acidic hydrothermal fluids.
5.5.2. Cassiterite solubility in water
The experimental data of cassiterite solubility in water are com-
piled in Fig. 6. Kovalenko et al. (1986) derived the tin contents in
water under two different f O2 levels, one buffered by f O2 = NNO
and the other buffered by f O2 = MM. The latter f O2 gave a high oxy-
gen fugacity of logf O2 =
0.22 bar at 500 °C and 100 MPa, close to
that under unconstrained f O2 conditions. Kokh et al. (2017) con-
ducted solubility experiments under f O2 = PPM. The remaining four
Fig. 6. The available solubility data of cassiterite in water under hydrothermal conditions. Although several major discrepancies exist in these seven groups of experimental
data (see the text), cassiterite solubility in water at 100–500 °C does not exceed 1 ppm, indicating that either aqueous Sn(II) or Sn(IV) hydroxides play a minor role in
transporting tin in mineralizing fluids.
9
Geoscience Frontiers 14 (2023) 101624
groups of data were conducted under unconstrained f O2 conditions
(Klintsova and Barsukov, 1973; Liu and Chen, 1986; Sorokin and
Dadze, 1994; Amaya et al., 1997). It should be noted that the solu-
bility data in Sorokin and Dadze (1994) contain those of Dadze
et al. (1981), so the latter is not shown here.
The comparisons suggest that several discrepancies exist
among these experimental data (see Fig. 6). First, Liu and Chen
(1986) substantially underestimated cassiterite solubility at room
temperature and higher temperatures for unknown reasons. Sec-
ond, the negative correlation between tin contents and tempera-
ture in Klintsova and Barsukov (1973) is problematic because of
a positive correlation suggested by most other data. Third, the
influences of f O2 on tin contents are contradictory, with an inde-
pendent relation suggested by the data of Kovalenko et al. (1986)
and a positive correlation suggested by the difference between
the data of Sorokin and Dadze (1994) and Kokh et al. (2017).
Despite these inconsistencies, the total contents of both Sn(II)
and Sn(IV) hydroxides under tin-mineralizing conditions do not
exceed 1 ppm; therefore, aqueous tin hydroxides can be safely
ignored.
5.6. Sn(II) chloride and mixed hydrolytic complexes
Both SnCl+ and SnCl2(aq) are stable in aqueous solutions at
25 °C (Séby et al., 2001; Cigala et al., 2012). Séby et al. (2001)
and Gamsjäger et al. (2012) derived their formation constants at
25 °C, 0.1 MPa, and infinite dilution from available experimental
data using specific interaction theory (SIT):

2
n
Sn2þ þ nCl
¼ SnCln ðn ¼ 1
4Þ ð6Þ
Their results are close to the voltammetric measurements con-
ducted by Cigala et al. (2012). The presence of SnCl+ and SnCl2(aq)
under hydrothermal conditions is also supported by different ana-
lytical techniques (e.g., solubility experiments, spectrophotometry,
X. Liu, P. Yu and C. Xiao
and molecular dynamics simulations) (Pabalan, 1986; Wilson and
Eugster, 1990; Müller and Seward, 2001). Recent molecular
dynamics simulations of Wang et al. (2021) also indicate that
SnCl2(aq) is stable at 500–700 °C and 150 MPa.
SnCl
3 is another major Sn(II) chloride complex at room temper-
ature (Cigala et al., 2012; Séby et al., 2001). The existence of SnCl
3
in solutions at 350 °C is supported by different analytical tech-
niques (e.g., EXAFS, solubility, spectrophotometry, Raman spectra,
and molecular dynamic simulations) (Pabalan, 1986; Sherman
et al., 2000; Müller and Seward, 2001; Chou et al., 2021; Wang
et al., 2021), while its presence at higher temperatures (400–
700 °C) is not supported by solubility experiments (Wilson and
Eugster, 1990; Duc-Tin et al., 2007). Recent molecular dynamic
simulations also suggest that the dominant Sn(II) chloride complex
at 500–700 °C is SnCl2(aq) rather than SnCl
3 (Wang et al., 2021). It
should be noted that the in situ Raman spectra of Sn(II)-Cl at 500–
600 °C identified by Schmidt (2018) (see his Figs. 4 and 5) are sim-
ilar to those of SnCl
3 identified by Chou et al. (2021) at 300 °C (see
their Fig. 3), indicating the presence of SnCl
3 in the experiments of
both studies. From the above analysis, SnCl
3 should be considered
under tin-mineralizing conditions.
The presence of SnCl2
4 in aqueous solutions under room and
hydrothermal conditions is more controversial than other Sn(II)
chloride complexes. Gamsjäger et al. (2012) argued that SnCl2
4 is
likely present at high chloride concentrations, whereas Cigala
et al. (2012) did not find SnCl2
4 in solutions with 2.44 molal Cl
at 25 °C. Pabalan (1986) and Sherman et al. (2000) identified SnCl2- 4


in aqueous saline solutions at temperatures reaching 350 °C from
solubility experiments and EXAFS spectroscopic data, respectively,
while Wang et al. (2021) proposed from molecular dynamic simu-
lations that SnCl2
4 has a low stability at 55 °C and is unstable at
300 °C. The solubility data at higher temperatures (400–700 °C)
of Wilson and Eugster (1990) and Duc-Tin et al. (2007) denied
the presence of substantial concentrations of SnCl2

4 , and Müller
and Seward’s (2001) spectrophotometric data did not detect SnCl2
4
in concentrated chloride solutions (reaching 3 molal) above 150 °C.
Müller and Seward (2001) inferred that Pabalan (1986) data may
have been affected by hydrolyzed Sn(II) species and that the Sn
(II) solutions used by Sherman et al. (2000) may have been partly
oxidized. From the analysis above, SnCl2

4 is negligible under tin-
mineralizing temperatures.
Hydrolyzed Sn(II) can also form mixed hydroxy–chloride com-
plexes (e.g., SnOHCl) at 25 °C when Cl is available (see references
in Müller and Seward, 2001; Séby et al., 2001; Cigala et al.,
2012). Only neutral SnOHCl was reported to exist at 25 °C (see
Table 1 in Cigala et al., 2012). SnOHCl can account for 60% of the
total Sn(II) content at pH  4.5 but is less important than Sn(II)
chloride complexes at more acidic pH levels (cf. Cigala et al.,
2012). SnOHCl was interpreted to be a major tin-bearing complex
under neutral pH levels at higher temperatures (Kovalenko et al.,
1986; Li, 1988; Taylor and Wall, 1993). Duc-Tin et al. (2007) used
SnOHCl as one of two potential tin-bearing complexes in their HCl-
bearing experiments at 700 °C. At alkaline pH levels, the charged
species Sn(OH)2Cl
was reported to exist by Kovalenko et al.
(1992), while Taylor and Wall (1993) argued that alkali chloride
complexes (e.g., KSnOHCI2) may be important in fluids with high
concentrations of alkali chloride. Until now, there has been no
in situ experimental evidence for mixed hydroxy–chloride com-
plexes in acidic hydrothermal fluids (e.g., Chou et al., 2021;
Wang et al., 2021).
The above analysis suggests that Sn(II) chloride complexes in
tin-mineralizing fluids exist mainly as SnCl+, SnCl2(aq), and SnCl
3.
The standard molar properties and revised HKF model parameters
of these three complexes were estimated from the correlation algo-
rithms in Supplementary Data 1. To enable comparisons with the
data of Müller and Seward (2001) and Barsukov et al. (1990), the
10
Geoscience Frontiers 14 (2023) 101624
logK values of Reaction (6) (n = 1, 2, and 3) were calculated from
their HKF model parameters and those of Sn2+ and Cl
.
The experimental logK values derived by Müller and Seward
(2001) are 1–4 orders of magnitude lower than those calculated
in the present study and Barsukov et al. (1990) from their revised
Ryzhenko–Bryzgalin parameters, and their differences increase
with temperature (Fig. 7). The logK values of Müller and Seward
(2001) are possibly problematic for the following reasons. First,
the RB parameters of Barsukov et al. (1990) could reproduce the
solubility data of Wilson and Eugster (1990) under f O2 = NNO (cf.
Ryzhenko et al., 1997), so using the logK values of Müller and
Seward (2001) would not reproduce the data of Wilson and
Eugster (1990). Second, Müller and Seward (2001) proposed from
thermodynamic calculations that SnCl
3 was the dominant Sn(II)
chloride complex at 400 °C, 50 MPa, 4.2 molal NaCl, and
pH = 2.4. This is inconsistent with the dominance of SnCl2(aq)
found by Wang et al. (2021). Third, to support the validity of their
logK values, Müller and Seward (2001) calculated the tin content at
400 °C, 50 MPa, 4.2 molal NaCl, and pH = 2.4 to be 450 ppm, close
to that (381 ppm) of fluid inclusions from the Huanuni tin deposit,
Bolivia (Müller et al., 2001). However, the pH value used by Müller
and Seward (2001) is considerably more acidic than that of the
fluid inclusions (see Section 2). As our thermodynamic modeling
results show later, the tin solubility in such acidic fluids is approx-
imately two orders of magnitude higher than the value derived by
Müller and Seward (2001).
The systematic difference in logK values of SnCl+ between this
study and Barsukov et al. (1990) does not exceed one order of mag-
nitude, but the differences for SnCl2(aq) and SnCl
3 at temperatures
over 200 °C reach 1–2 orders of magnitude. The reasons for these
large differences will be discussed later.
5.7. Sn(IV) chloride complexes and mixed hydrolytic species
Sn(IV) chloride complexes SnCl4
n n (n = 1–6) in aqueous solu-
tions are stable at room temperature (Taylor and Coddington,
1992; Gamsjäger et al., 2012). Taylor and Coddington (1992)
reported the NMR and Raman spectra data of SnCl4
n n (n = 1–6)
at 20–60 °C, building a basis for the Raman peak assignments in
later studies. The spectrophotometric data of Gajda et al. (2009)
suggest that the main Sn(IV) chloride complexes in solutions >0.1


molal Cl at 25 °C are SnCl2
6 , SnCl5 , and SnCl4(aq). The dominance
of SnCl2
6 is supported by the EXAFS spectroscopic data of Sherman
et al. (2000) at 25–270 °C. In contrast, Chou et al. (2021) did not
identify SnCl2
6 from in situ Raman spectra of SnCl4 + HCl solutions
at 30 °C and the corresponding Sn(IV)–Cl band is composed of 55%
SnCl
+
5 , 26% SnCl4(aq), and 19% SnCl3 (see their supplementary
information of S-5). Chou et al. (2021) used 0.5 molal SnCl4 and
0.5 molal HCl in their solutions, which are more acidic than those
(0.01 molal SnCl4, 0.11 molal HCl, and 2 molal NaCl) of Sherman
et al. (2000). Therefore, the availability of Cl in these two groups
of experiments cannot explain their great discrepancy on the main
Sn(IV) chloride complexes and more reliable experimental data are
needed in future.
Five groups of solubility data of cassiterite under oxidized
hydrothermal conditions are available in the literature. Dadze
et al. (1981) and Li (1988) conducted their experiments under
unconstrained f O2 conditions. The f O2 ¼ MM used by Kovalenko
et al. (1986) gave an oxygen fugacity of logf O2 =
0.22 bar at
500 °C and 100 MPa, while the solutions used by Wilson and
Eugster (1990) were buffered by the hematite–magnitite mineral
assemblage. Schmidt (2018) did not used mineral buffers, thus
the precise f O2 levels in his experiments are unknown (probably
not far from NNO in the experiments in which Ar + CH4 gas was
used as flushing gas (Schmidt et al., 2021)).
X. Liu, P. Yu and C. Xiao
Fig. 7. Comparisons between experimental and calculated logK values of SnCl+,
SnCl2(aq), and SnCl

3 . The experimental logK values derived by Müller and Seward
(2001) are 1–4 orders of magnitude lower than those calculated by this study and
Barsukov et al. (1990) from their revised Ryzhenko-Bryzgalin parameters. The
reasons for these major discrepancies are possibly because the spectrophotometric
data of Müller and Seward (2001) underestimated the logK values of Sn(II) chloride
complexes.
11
Geoscience Frontiers 14 (2023) 101624
The cassiterite solubility data in the same group increase with
temperature and HCl concentrations in solutions, but the solubil-
ity data among different groups under the same conditions differ
from each other (Fig. 8). For example, the solubility data in 0.1
molal HCl solutions of Dadze et al. (1981) exceed those of Li
(1988) except at 200 °C (Fig. 8). In contrast, the data of Dadze
et al. (1981) in 0.01 molal HCl solutions are approximately two
orders of magnitude lower than those of Li (1988). The reasons
for their discrepancies are unknown and at least one group of
experimental data are problematic. Fig. 9a shows that the data
of Kovalenko et al. (1986) at 500 °C are systematically lower than
those of Li (1988) and Wilson and Eugster (1990), the latter of
which are consistent with Schmidt (2018) if the influences of
fluid pressure are assumed to be minor (Fig. 9c). Note that most
data of Kovalenko et al. (1986) are lower than the detection limit.
Therefore, only the data of Wilson and Eugster (1990) and
Schmidt (2018) can be trusted.
The dominant Sn(IV) chloride complexes in high-temperature
acidic solutions are controversial. SnCl+3 was interpreted by
Wilson and Eugster (1990) to be the dominant tin species in HCl
solutions at 500–600 °C, whereas Schmidt (2018) proposed that
the most abundant complex at the same temperatures was SnCl4(-
aq) with additional SnCl+3. The HCl molalities (0.17–4.64 molal)
used by Wilson and Eugster (1990) are slightly wider than those
(1.63–4.16 molal) of Schmidt (2018). The Raman spectra of SnClo4(-
aq) and SnCl+3 were identified by Schmidt (2018), while the coordi-
nation number of Cl around Sn4+ was calculated by Wilson and
Eugster (1990) using nonlinear least squares regressions. From
the fitting results of Wilson and Eugster (1990) (see their Fig. 6),
the variation for fitting SnCl+3 to the experimental data is slightly
lower than that for SnCl4(aq). Accepting the in situ evidence of
Schmidt (2018), we interpreted that a great amount of SnCl4(aq)
existed in the solutions of Wilson and Eugster (1990), producing
the average coordination number of Cl
around Sn4+ between 3
and 4. The existence of Sn(II) chloride complexes (e.g., SnCl2(aq))
in the solutions of Wilson and Eugster (1990) also lowered the
Fig. 8. Major discrepancies of cassiterite solubility in acidic solutions under
unconstrained f O2 conditions. The solubility data in 0.1 molal HCl solutions of
Dadze et al. (1981) exceed those of Li (1988) except the point at 200 °C, while the
data of Dadze et al. (1981) in 0.01 molal HCl solutions are approximately two orders
of magnitude lower than those of Li (1988). These discrepancies suggest that at
least one group of experimental data are problematic.
X. Liu, P. Yu and C. Xiao
Fig. 9. The experimental and calculated cassiterite solubility data in HCl solutions under f O2 ¼ HM. (a, c) the calculated solubility data (model 1a) at 500 and 600 °C are
consistent with the experimental data of Wilson and Eugster (1990); (b, d) the dominant tin species in most cases is SnCl+3, followed by SnCl2(aq).
average coordination number. The above analysis suggests that the
major Sn(IV) chloride complexes under hydrothermal acidic condi-
tions are possibly SnCl4(aq) and SnCl+3, and the empirical logK
equation of SnCl+3 fitted by Wilson and Eugster (1990) possibly
integrates the contributions of these two Sn(IV) chloride
complexes.
Mixed hydroxy–chloride complexes (e.g., Sn(OH)3Cl and
SnOHCl3) were also interpreted to be major Sn(IV)-bearing species
in HCl solutions under oxidized hydrothermal conditions
(Kovalenko et al., 1986; Li, 1988; Sorokin and Dadze, 1994).
Kovalenko et al. (1986) tried to explain their solubility data using
SnOHCl3, but their least squares fitting was not satisfactory. Li
(1988) proposed from his solubility data that mixed hydroxy–chlo-
ride complexes (e.g., Sn(OH)3Cl) were the dominant Sn(IV)-bearing
complex in solutions of HCl < 0.1 molal, while the dominant com-
plex in solutions of >0.1 molal HCl became SnCl4(aq). Sorokin and
Dadze (1994) also proposed that Sn(OH)3Cl may be important in
HCl solutions. However, those mixed complexes were identified
neither by the EXAFS spectroscopic data of Sherman et al. (2000)
nor by the in situ Raman spectra of Chou et al. (2021). According
to Pearson’s hard/soft acid/base principle (Pearson, 1963), Sn4+ (a
hard acid) bonds preferentially with OH
(a hard base) compared
to Cl
(a borderline base). The Cl concentrations of the solutions
used by Li (1988) and Sorokin and Dadze (1994) did not exceed
1 molal, lower than those of Sherman et al. (2000) and Chou
et al. (2021). Therefore, the ligand numbers of OH
and Cl
of
stable Sn(IV) hydroxy–chloride complexes may depend on the
availability of Cl and further experiments are needed to support
or reject their existence.
12
Geoscience Frontiers 14 (2023) 101624
6. Thermodynamic modeling results for cassiterite solubility
Cassiterite solubility under hydrothermal conditions was mod-
eled using a tin speciation model consisting of SnCl+, SnCl2(aq),
SnCl
+ 2+ 4+
3 , SnCl3, Sn , and Sn . Despite the dispute on Sn(IV) chloride
complexes (see Section 5.7), the empirical equation for the logK of
SnCl+3 fitted by Wilson and Eugster (1990) was provisionally used
to represent the contribution of Sn(IV) chloride complexes to cas-
siterite solubility, especially under oxidized conditions. Table 5
lists all the chemical reactions in the models and Table 6 shows
the charge and mass balance equations. The modeling results are
listed in Supplementary Data 3.
6.1. Cassiterite solubility in HCl solutions and f O2 = HM (Model 1a)
Cassiterite solubility in HCl solutions at 500–600 °C, 150 MPa,
and f O2 = HM was first modeled to compare with the corresponding
solubility data of Wilson and Eugster (1990) and test the thermo-
dynamic parameters of aqueous tin species. Their solubility exper-
iments correspond to the SnO2–HCl–H2O chemical system (Model
1a; see Tables 5 and 6). The calculated tin contents at 500 °C are
consistent with the experimental data of Wilson and Eugster
(1990) (Fig. 9a), and the SnCl+3 contents exceed Sn(II) chloride com-
plexes by a few orders of magnitude (Fig. 9b), except in 0.01 molal
HCl solutions. The calculated tin contents at 600 °C are slightly
greater than the experimental data of Wilson and Eugster (1990)
(Fig. 9c), and the dominant tin species in >0.1 molal HCl solutions
remains SnCl+3 (Fig. 9d). Note that the concentrations of Sn4+ in all
models are zero.
X. Liu, P. Yu and C. Xiao Geoscience Frontiers 14 (2023) 101624

Table 5
Chemical reactions in the thermodynamic models.

Number Chemical reactions Model numbers Source of logK

+

1 H2O = H + OH 1a, 1b, 2a, 2b, 2c a
2 H+ + Cl
= HCl(aq) 1a, 1b, 2a, 2b, 2c a
3 SnO2(s) + 2H+ = Sn2+ + H2O + 0.5O2(g) 1a, 1b, 2a, 2b, 2c a, b
4 Sn2+ + 2H+ + 0.5O2(g) = Sn4+ + H2O 1a, 1b, 2a, 2b, 2c a, b
5 SnO2(s) + 4HCl(aq) = SnCl+3 + Cl
+ 2H2O 1a, 1b, 2a, 2b, 2c a, b
6 Sn2+ + Cl
= SnCl+ 1a, 1b, 2a, 2b, 2c a, b
7 Sn2+ + 2Cl
= SnCl2(aq) 1a, 1b, 2a, 2b, 2c a, b
8 Sn2+ + 3Cl
= SnCl
3 1a, 1b, 2a, 2b, 2c a, b
9 Na+ + OH
= NaOH(aq) 2a, 2b, 2c a, c
+

10 Na + Cl = NaCl(aq) 2a, 2b, 2c a, c
11 4Fe3O4(magnetite) + O2(g) = 6Fe2O3(hematite) 1a a
12 Ni(s) + 0.5O2(g) = NiO(s) 1b, 2b a
13 3SiO2(quartz) + 2Fe3O4(magnetite) = 3Fe2SiO4(fayalite) + O2(g) 2a a

a, SUPCRT; b, this study; c, Miron et al. (2016). The letters in the brackets: s, solid phase; aq, aqueous phase; g, gaseous phase.

Table 6 6.3. Cassiterite solubility in the NaCl–HCl–H2O chemical system

The charge and mass balance equations used in the models.

Number Charge and mass balance Equations Model

relations numbers
P P
1 Charge balance ½cations ¼ ½anions 1a, 1b, 2a,
2b, 2c
2 A given total molality of – 1a, 1b, 2a,
Cl 2b, 2c
3 A fixed pH mHþ =10
pH =cHþ 2a, 2b
4 An initial HCl content – 2c
5 A fixed oxygen fugacity – 2c
mHþ represents the molality of Hþ and cHþ is the activity coefficient of Hþ .
6.2. Cassiterite solubility in HCl solutions and f O2 = NNO (Model 1b)
Cassiterite solubility in HCl solutions at 400–700 °C and
f O2 = NNO was modeled to compare with the solubility data of
Kovalenko et al. (1986), Wilson and Eugster (1990) and Duc-Tin
et al. (2007). The only difference between this model and the pre-
vious one is the mineral assemblage–buffered f O2 .
The calculated solubilities at 400 °C are slightly smaller than the
corresponding experimental data of Wilson and Eugster (1990)
(Fig. 10a). Fig. 10b shows that SnCl2(aq) is the dominant aqueous
species, and the contents of other Sn(II) and Sn(IV) chloride com-
plexes in >1 molal HCl solutions are also appreciable. The calcu-
lated solubilities at 500 °C are close to the data of Wilson and
Eugster (1990) and Kovalenko et al. (1986) (Fig. 10c). The domi-
nant tin species depends on the initial HCl contents in the solu-
tions, SnCl2(aq) in <0.1 molal HCl solutions and SnCl+3 in >0.1
molal HCl solutions (Fig. 10d).
The calculated solubility data at 600 °C and 150 MPa are also
slightly smaller than the corresponding experimental data of
Wilson and Eugster (1990) except the data point in 0.302 molal
HCl solution (Fig. 10e). This experimental point was interpreted
to be abnormal because it exceeds the tin concentrations both in
0.614 molal and 1.11 molal HCl solutions. The dominant tin species
is SnCl2(aq) in 0.1 molal HCl solutions and changes to SnCl+3 in
>0.15 molal HCl solutions (Fig. 10f).
Fig. 10g compares the experimental and calculated solubility
data at 700 °C and 140 MPa. The calculated values in >2 molal
HCl solutions are close to the experimental data of Duc-Tin et al.
(2007). However, the experimental data in 1 molal HCl solutions
are systematically higher than our calculated values, and their dif-
ference in 0.1–0.3 molal HCl solutions exceeds one order of magni-
tude. The dominant tin species is SnCl2(aq) in 3 molal HCl
solutions and changes to SnCl+3 in >3 molal HCl olutions (Fig. 10h).
13
The cassiterite solubility under tin-mineralizing conditions was
modeled in this section. To better compare the in situ tin contents
of fluid inclusions from typical Sn–W and W–Sn deposits (Fig. 2),
cassiterite solubility in the SnO2–NaCl–HCl–H2O chemical system
was calculated under the following conditions: 300–500 °C, 50–
150 MPa, 2 molal NaCl (1.7 molal NaCl = 10 wt.%), and pH = 3–4.
Two mineral assemblage–buffered f O2 levels were considered in
two models, f O2 = QFM in Model 2a and f O2 = NNO in Model 2b.
In addition to aqueous tin species, other species in these two mod-
els include H+, Cl
, HCl(aq), Na+, NaOH(aq), and NaCl(aq).
The tin contents at 400 °C, 50 MPa, 4.2 molal NaCl, and pH = 2.4
were calculated for comparison with the calculations of Müller and
Seward (2001) (see the second last paragraph in section 5.6). Under
these conditions, the tin contents were calculated to be
31,479 ppm under f O2 = NNO and 54,511 ppm under f O2 = QFM,
approximately two orders of magnitude higher than the value
(450 ppm) derived by Müller and Seward (2001) and the tin con-
tent (381 ppm) of fluid inclusions from the Huanuni tin deposit,
Bolivia (Müller et al., 2001).
The contour maps under f O2 = NNO and QFM (logarithmically
transformed to base 10) in Fig. 11 show that cassiterite solubility
under tin-mineralizing conditions increases with increasing tem-
perature and decreasing pH. Cassiterite solubility is slightly nega-
tively correlated with fluid pressure, and the negative influence
of fluid pressure is stronger at higher temperatures. The tin content
range (10–1000 ppm) of fluid inclusions is also shown in Fig. 11
(see the dotted lines) for better comparisons. The calculated solu-
bility data at a fixed pH = 4 exceed 10 ppm only at temperatures
over 350–380 °C, depending on the f O2 levels (Fig. 11a and c).
When the fluid acidity decreases to pH = 3, the fluids at 300 °C
can dissolve 10 ppm tin (Fig. 11b and d).
The f O2 levels buffered by a mineral assemblage increase with
increasing temperature (Fig. 1), so this variable is temperature-
dependent. Neutral pH levels also depend on temperature, and fix-
ing pH (i.e. the activity of H+) but increasing temperature would
elevate the activity of OH
. To avoid these problems, we used an
initial HCl content in Model 2c and the f O2 levels vary from QFM
to HM. Using HCl contents also enables comparisons between
our modelling results and the available experimental data. The
HCl contents of magmatic–hydrothermal fluids are poorly con-
strained, especially for tin-mineralizing fluids. Piccoli et al.
(1999) used aplite and apatite chemistry to constrain the HCl con-
tents to be approximately 0.02 molal. Note that no mineralization
occurs around the two granites studied by Piccoli et al. (1999) (cf.
Kistler and Swanson, 1981), so tin-mineralizing fluids possibly
X. Liu, P. Yu and C. Xiao Geoscience Frontiers 14 (2023) 101624

Fig. 10. Comparisons between calculated and experimentally determined cassiterite solubilities in HCl solutions under 400–700 °C and f O2 ¼ NNO. The calculated solubility
data (model 1b) are consistent with most experimental data of Kovalenko et al. (1986), Wilson and Eugster (1990), and Duc-Tin et al. (2007). The dominant aqueous tin
species is SnCl2(aq), but the contents of tin(IV) chloride complexes are also appreciable and can exceed SnCl2(aq) in high HCl solutions.

14
X. Liu, P. Yu and C. Xiao Geoscience Frontiers 14 (2023) 101624

Fig. 11. The contour maps of cassiterite solubility (ppm) at a fixed salinity and pH. (a) pH = 4 and f O2 ¼ Q FM (model 2a); (b) pH = 3 and f O2 ¼ Q FM (model 2a); (c) pH = 4 and
f O2 ¼ NNO (model 2b); (b) pH = 3 and f O2 ¼ NNO (model 2b). The solubility data have been logarithmically transformed (base 10). The area circled by dotted lines represents
the tin content range (10–1000 ppm, see Fig. 2) of fluid inclusion from typical tin-tungsten deposits. Approximately half of the cassiterite solubilities at pH = 4 are
considerably lower than the in situ tin concentrations of fluid inclusions, while those at pH = 3 are generally higher than tin concentrations from tin-mineralizing fluids. The
solubilities at the right and lower corners are not calculated because the HKF model is not applicable in regions of low water density (<0.35 g cm
3).

have higher HCl contents. HCl contents of 0.1 molal and 0.5 molal
are used in the Model 2c.
The contour maps of Fig. 12a and b illustrate that the fluid
pH levels mostly lie 1.6–3.4 in 0.1 molal HCl solutions at 300–
500 °C and f O2 = QFM–HM, and they decrease to 1.0–3.0 in 0.5
molal HCl solutions. These pH levels are 2–3 log units lower
than the values (pH = 4–6 in section 2) constrained by fluid-
mineral equilibrium. Consequently, cassiterite solubility in 0.1
molal HCl solutions under f O2 = QFM–NNO reach thousands of
ppm (Fig. 12c), while the solubilities under higher f O2 levels
(HM) decrease to hundreds of ppm. This negative correlation
between cassiterite solubility and f O2 levels also exist in 0.5
molal HCl solutions. From Fig. 12c and d, cassiterite solubility
increases with temperature and HCl contents and decreases with
f O2 levels. The molar ratios of Sn(II) against Sn(IV) were calcu-
lated to show their relative importance in transporting tin in
hydrothermal fluids (Fig. 12e and f). The Sn(II)/Sn(IV) molar
ratios are negatively correlated to f O2 levels, temperature, and
HCl contents. Sn(IV) in 0.1 molal HCl solutions exceeds Sn(II)
only at >420 °C and f O2 levels 2–3 log units greater than NNO,
while the dominance of Sn(IV) over Sn(II) in 0.5 molal HCl
15
solutions occurs at lower temperatures (>380 °C) and lower f O2
levels (from slightly higher than NNO to HM).
7. Discussion
7.1. Consistency and uncertainties of thermodynamic data of aqueous
Sn(II) and Sn(IV) species
The internal consistency of thermodynamic data is vital for con-
fident calculations of aqueous geochemical processes (Tutolo et al.,
2014; Wolery and Jové Colón, 2017). Most thermodynamic data in
the models come from the SUPCRT database, while the empirical
logK equation of SnCl+3 in the models was fitted by Wilson and
Eugster (1990) from their solubility data. This compromise was
made because of the lack of more reliable thermodynamic data
for Sn(IV) chloride complexes. The internal consistency between
cassiterite and aqueous tin species should be examined after reli-
able thermodynamic parameters of major Sn(IV) chloride com-
plexes are available.
The uncertainties of our modeling results stem from the corre-
lation algorithms and the empirical equation of Wilson and Eugster
X. Liu, P. Yu and C. Xiao Geoscience Frontiers 14 (2023) 101624

Fig. 12. The contour maps of pH (a, b), cassiterite solubility (c, d), and Sn(II)/Sn(IV) molar ratios (e, f) under 300–500 °C and f O2 levels from QFM to NNO. The fluid pressure
and the concentrations of NaCl are fixed, and the differences between the left and right maps lie in the HCl contents (0.1 molal and 0.5 molal). The three dotted lines in each
contour map represent f O2 ¼ HM, NNO, and QFM from the top down. The solubility data and Sn(II)/Sn(IV) molar ratios have been logarithmically transformed (base 10).

(1990). Sverjensky et al. (1997) identified three major sources of
uncertainty caused by the correlation algorithms, the logK value
at 25 °C and 1 bar, the equation for the revised HKF model param-
eters (Eqs. A5–A12 in Supplementary Data 1), and the equations
among the standard molar properties (Eqs. A13–A20 in Supple-
mentary Data 1). For Sn(II) chloride complexes, logK values at
25 °C and 1 bar are reliable (Séby et al., 2001; Cigala et al., 2012;
Gamsjäger et al., 2012), and the remaining two sources may lead
to an uncertainty for their logK values at 500 °C by no more than
one log unit (see Section 9 in Sverjensky et al., 1997). The compar-
isons made by Sverjensky et al. (1997) showed that the discrepan-
cies between the experimental and calculated logK values for
chloride complexes of bivalent cations are well within the esti-
mated uncertainties.

16
X. Liu, P. Yu and C. Xiao
Wilson and Eugster (1990) derived the empirical equation for
the logK of Sn(IV) chloride complexes from the experimental data
at 500 and 600 °C. Whether their empirical equation remains valid
at other temperatures is unknown, but the comparisons shown in
Figs. 9 and 10 suggest their empirical equation, together with the
revised HKF model parameters of Sn(II) chloride complexes, can
reproduce most experimental solubility data at 400–700 °C. The
following comparisons suggest that extending the empirical equa-
tion for SnCl+3 to 300 °C possibly underestimates the contents of Sn
(IV) chlorides. From in situ Raman spectra of 0.5 molal SnCl4 + 0.5
molal HCl solution at 300 °C and f O2 = QFM (i.e. P H2 = 1.3 bar), Chou
et al. (2021) identified that almost all the Sn(IV) species were con-
verted to Sn(II) within 48 hours, consistent with the dominance of
Sn(IV) in our modelling results under similar conditions (see
Fig. 12f). However, they identified Raman spectra of Sn(IV) at
300 °C and f O2 = NNO (i.e. P H2 = 0.2 bar), indicating notable con-
tents of Sn(IV) chloride complexes. In contrast, the Sn(IV) content
in our modelling results is approximately seven orders of magni-
tude lower than the Sn(II) content, leaving a minor role of Sn(IV)
in the total tin content. Chou et al. (2021) did not detect cassiterite
precipitation after the solutions having 0.5 molal SnCl4 were
heated to 300 °C, which suggests that their solutions having 0.5
molal Sn at 300 °C were not saturated with cassiterite. Under the
experimental conditions of Chou et al. (2021), we calculated the
cassiterite solubility to be 0.13 molal at f O2 = NNO and 0.19 molal
at f O2 = QFM, accounting for 26% and 30% of the tin contents in
solutions used by Chou et al. (2021). Therefore, more cassiterite
solubility data under <500 °C and oxidized conditions are needed
to refine the empirical equation of Wilson and Eugster (1990).
Ryzhenko et al. (1997) reported revised Ryzhenko–Bryzgalin
model parameters of aqueous Sn(II) and Sn(IV) chlorides and
hydroxides, but their RB model parameters failed to reproduce
the data of Wilson and Eugster (1990) under f O2 = HM. One of pos-
sible reasons for the failure is that their RB model parameters of
aqueous Sn(IV) chlorides were estimated from the experimental
data of Kovalenko et al. (1986). From Fig. 9a, most data of
Kovalenko et al. (1986) are lower than the detection limit for
unknown reasons, and their data are systematically lower than
those of Wilson and Eugster (1990).
7.2. The roles of Sn(II) and Sn(IV) in hydrothermal fluids
It has long been accepted that tin in mineralizing fluids is trans-
ported mainly as Sn(II) chloride complexes (Lehmann, 1990, 2021).
However, this earlier point of view is challenged by recent in situ
high-temperature experiments and molecular dynamic simula-
tions (Schmidt, 2018; Chou et al., 2021; Wang et al., 2021). Wang
et al. (2021) argued from Sn isotope variations in their molecular
dynamic simulations and natural cassiterite that tin in mineraliz-
ing fluids was transported mainly as Sn(IV) species, opposing the
earlier view of Sn(II) dominance. Schmidt (2018) proposed from
in situ Raman data that Sn(IV) chloride complexes are capable of
transporting considerable amounts of tin and are possibly preva-
lent tin–transporting species. The in situ Raman data of Chou
et al. (2021) suggest that notable contents of both Sn(II) and Sn
(IV) exist in solutions under f O2 ¼ NNO. Our modeling results sug-
gest that the roles of Sn(II) and Sn(IV) in transporting tin in acidic
hydrothermal fluids depend on f O2 , temperature, and HCl contents
(Figs. 9 and 10).
The f O2 levels are one of the key variables controlling the
valence of tin in acidic saline fluids. As the f O2 rises from QFM to
HM at a constant temperature, the molar ratios of total Sn(II) to
Sn(IV) can decrease by approximately three orders of magnitude
(Fig. 12e and f). Under a fixed f O2 level, the molar ratios of total
17
Geoscience Frontiers 14 (2023) 101624
Sn(II) to Sn(IV) would decrease by approximately one order of
magnitude as the fluids at 400–500 °C cool by 100 °C (Fig. 12e
and f). HCl contents also alter the roles of Sn(II) and Sn(IV) in trans-
porting tin. Our modeling results indicate that Sn(IV) chloride com-
plexes are also major species in high HCl solutions (Figs. 9–12). The
influence of HCl contents on the valence of major tin species can be
interpreted by the chemical reaction:
SnCl2 (aq) + 0.5O2 (g) + 2HCl(aq) = SnCl4 (aq) + H2 O ð7Þ
HCl is less dissociated under hydrothermal conditions than at
room temperature, so it is predominantly associated HCl(aq) in
the model conditions (see Supplementary Data 3). According to
Le Châtelier’s Principle, a higher content of HCl in fluids would
make the equilibrium shift to the right side of Reaction (7), increas-
ing the contents of Sn(IV) chloride complexes. Therefore, a major
part of tin is possibly transported as Sn(IV) chloride complexes at
an early mineralization stage, supporting the proposal of Schmidt
(2018). This is also a major supplement to the earlier view of the
dominance of Sn(II) chloride complexes in tin-mineralizing fluids.
Wang et al.’s (2021) simulation results can be interpreted by two
possible cases. The first case is that the cassiterite they used for
Sn isotope analysis was precipitated from high-temperature and
high-HCl fluids although the cassiterite formation temperatures
are unknown. The second case is that their cassiterite precipitated
from oxidized fluids. For hydrothermal experiments of tin specia-
tion and cassiterite solubility, the influences of HCl contents on
the valence of major tin species should be considered because
experimental HCl contents are commonly considerably greater
than those in natural hydrothermal systems (cf. Piccoli et al.,
1999).
Most solubility experiments of cassiterite under f O2 ¼ NNO
were intepreted using Sn(II) chloride complexes (Kovalenko
et al., 1986; Li, 1988; Wilson and Eugster, 1990; Duc-Tin et al.,
2007), but our modeling results under the same conditions suggest
that the main aqueous tin species would change to be Sn(IV) chlo-
ride complexes in high-HCl solutions (Fig. 10). Consequently,
ignoring Sn(IV) chloride complexes in the regression of solubility
experiments under f O2 ¼ NNO (the method used by Barsukov
et al. (1990)) would overestimate the logK values of Sn(II) chloride
complexes. This interprets why the logK values calculated by
Barsukov et al. (1990) are systematically greater than our calcu-
lated values (see Fig. 7 and the last paragraph of section 5.6).
7.3. Cassiterite precipitation mechanisms from hydrothermal fluids
Redox reactions are required for cassiterite precipitation in pre-
vious formation models (cf. Lehmann, 1990, 2021). From our mod-
eling results (Fig. 12e and f), the contents of Sn(IV) chloride
complexes are possibly appreciable when the mineralizing fluids
contain high contents of HCl and their temperatures are high.
These conditions are more easily satisfied at an early mineraliza-
tion stage. In this case, redox reactions are not necessary for pre-
cipitating cassiterite. Thus, our modeling results support Schmidt
et al. (2018, 2021), who proposed that redox reactions play a smal-
ler role than assumed in previous formation models. Also, even if
the f O2 levels are kept to be constant, simple cooling moves fluids
to more oxidized levels (e.g., from QFM to HM) and can decrease
cassiterite solubility by up to one order of magnitude. Therefore,
oxidizing agents are not necessary for precipitating cassiterite from
Sn(II)-dominated hydrothermal fluids. This can explain why
cassiterite-bearing quartz veins in many tin deposits are hosted
by sandstone or quartzite that do not provide oxidizing agents
(Rozendaal et al., 1995; Liu et al., 2021; Li et al., 2022). Besides, cas-
siterite precipitation from acid hydrothermal fluids is also caused
by pH neutralization (e.g., greisens) (Fig. 11) and an increase in
X. Liu, P. Yu and C. Xiao
f O2 through redox reactions, while a drop in fluid pressure cannot
precipitate cassiterite from liquid fluids.
7.4. Incomplete buffering of mineralizing fluids by granitic rocks
Previous studies indicate that tin-mineralizing fluids have pH
levels of 4–6 (Patterson et al., 1981; Jackson and Helgeson,
1985b; Polya, 1989), which correspond to the pH levels of fluids
in equilibrium with the mineral assemblages of quartz–muscovite.
However, the calculated cassiterite solubilities at pH = 4 and
f O2 = QFM or NNO are substantially lower than the in situ tin con-
centrations of fluid inclusions from typical tin–tungsten deposits
(Fig. 11a and c). This discrepancy can be reconciled by the interpre-
tation that the pH range (4–6) constrained by mineral–solution
equilibrium may represent the postmineralization pH levels and
that the actual pH levels of mineralizing fluids should be more
acidic (pH < 4). This comparison between our modeling results
and tin contents in fluid inclusions also suggests that the mineral-
izing fluids forming these typical tin–tungsten deposits are incom-
pletely buffered by granitic rocks. This interpretation is consistent
with Heinrich (1990), who proposed from his thermodynamic
modeling that incomplete chemical buffering of mineralizing fluids
by granitic rocks is a prerequisite for transporting high concentra-
tions of tin from the source to the deposition sites. Although the Sn
(II) chloride complexes (e.g., SnCl2

4 ) used by Heinrich (1990) are
problematic (see section 4.7), the conclusion of Heinrich (1990)
remains reasonable. Therefore, fluid focusing through a confined
channel (such as a vein), if mineralizing fluids are available, is
vitally important for producing economic tin mineralization.
8. Conclusions
The standard molar properties and revised HKF model parame-
ters of five aqueous tin species were derived from the correlation
algorithms among these parameters, and the standard molar prop-
erties of cassiterite were optimized to internally consistent with
the available dataset. These estimated thermodynamic parameters
reproduced the experimental solubility data in acidic fluids under
f O2 = NNO and higher f O2 conditions. Then, cassiterite solubility in
the SnO2–NaCl–HCl–H2O chemical system was calculated under
typical tin–mineralizing conditions. Our modeling results provide
the following implications for tin transport and cassiterite precip-
itation mechanisms from hydrothermal fluids:
(1) The total contents of Sn (II and IV) hydroxide complexes do
not exceed 1 ppm under hydrothermal conditions, consider-
ably lower than the tin contents (10–1000 ppm) of fluid
inclusions from typical tin–tungsten deposits in the world.
(2) The roles of Sn(II) and Sn(IV) in transporting tin in acidic
hydrothermal fluids depend on f O2 , temperature, and HCl
contents. Sn(IV) chloride complexes can be major aqueous
tin species in high temperature and high-HCl fluids even
under reduced conditions (e.g., f O2 ¼ NNO), so a great
amount of Sn(IV) chloride complexes possibly exist in an
early mineralization. In this case, redox reactions are unnec-
essary for precipitating cassiterite.
(3) Even if the f O2 levels are constant, simple cooling can move
mineralizing fluids to more oxidized levels and cause cassi-
terite precipitation; therefore, oxidizing agents are not nec-
essary for cassiterite precipitation. A simple rise in oxygen
fugacity and acid neutralization also precipitate cassiterite
from acidic fluids, while a drop in fluid pressure does not.
(4) Oxidized hydrothermal fluids under f O2 ¼ HM can dissolve
as much tin as fluid inclusions of typical tin-tungsten depos-
its, but it requires fluids to contain more HCl contents than
18
Geoscience Frontiers 14 (2023) 101624
reduced fluids under f O2 ¼ QFM–NNO. These strict condi-
tions decrease the tin mineralization potential of oxidized
hydrothermal fluids.
(5) The calculated solubilities under the pH levels constrained
by mineral–solution equilibrium are considerably lower
than the tin contents in fluid inclusions, indicating that
tin-mineralizing fluids should be more acidic (pH < 4).
Incomplete chemical buffering of mineralizing fluids by
granitic rocks is necessary to carry high concentrations of
tin from the source to deposition sites.
CRediT authorship contribution statement
Xiangchong Liu: Conceptualization, Investigation, Methodol-
ogy, Data curation, Visualization, Funding acquisition, Software,
Validation, Writing – original draft, Writing – review & editing.
Pingping Yu: Visualization, Investigation, Resources. Changhao
Xiao: Conceptualization, Funding acquisition, Writing – review &
editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The work was financially funded by CGS Research Fund
(DZLXJK202103, DZLXJK202206, DZLXJK202203), a China Geologi-
cal Survey project (DD20230344), a Guizhou Provincial Science and
Technology Project (Qiankehezhicheng [2021]408), and a major
project of Guizhou Bureau of Geology and Mineral Resources
Exploration and Development (Qiandikuangkehe [2021]1). The
authors thanked Jeffrey Dick for his help in using the R package
CHNOSZ and Christoph Heinrich for sharing his database fitted
from the experimental data of Pabalan (1986). David Wesolowski
is thanked for his patient explanation of extrapolating logK at zero
ionic strength. The staff from National Geological Library of China,
especially Liu Hong, is appreciated for their help in finding the Rus-
sian publications used in this study. Christian Schmidt, Wang Xin-
song, and two anonymous reviewers are thanked for their
constructive comments that significantly improved the original
manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.gsf.2023.101624.
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