©2018 Society of Economic Geologists, Inc.

Economic Geology, v. 113, no. 8, pp. 1861–1883

Fluid Inclusion Studies in Opaque Ore Minerals: II. A Comparative Study of

Syngenetic Synthetic Fluid Inclusions Hosted in Quartz and Opaque Minerals
V. Casanova,1,† K. Kouzmanov,1 A. Audétat,2 M. Wälle,3,* N. Ubrig,4 M. Ortelli,1 and L. Fontboté1
1 Department of Earth Sciences, University of Geneva, CH-1205 Geneva, Switzerland
2 Bayerisches Geoinstitut, Universität Bayreuth, 95440 Bayreuth, Germany
3 Institute of Geochemistry and Petrology, Department of Earth Sciences, ETH Zurich, 8092 Zurich, Switzerland
4 Department of Quantum Matter Physics (DQMP) and Group of Applied Physics (GAP),
University of Geneva, CH-1211 Geneva, Switzerland

Abstract
Fluid inclusion studies give unique insights into physical conditions and composition of fluids involved in geo-
logic processes. Most studies to date are performed on transparent minerals. Near-infrared (NIR) microscopy
allows microthermometry to also be performed on minerals that are opaque to the visible light, such as pyrite,
hematite, wolframite, enargite, and stibnite. The main drawback of this technique is the underestimation of
the recorded phase-change temperatures with increasing light intensity—up to several hundred percent in the
case of ice-melting temperatures. Although this issue has been known for a decade, it is poorly understood. We
address this problem based on a systematic study of synthetic fluid inclusions in a variety of opaque minerals.
For the first time, fluid inclusions have been cosynthesized with success in quartz and opaque minerals.
Fracturing the host minerals by in situ quenching allowed for fluid-mineral equilibration prior to fluid inclusion
formation. In this study, we assess the impact of mineral intrinsic parameters, mainly absorption and thermal
conductivity, and experimental settings (light source operative power, diaphragm aperture, and the use of fil-
ters) on recorded phase-change temperatures. We show that these are underestimated due to local overheating
of the sample caused by radiative heating from the light source. It affects all minerals, and the extent of the
temperature shift of the observed phase changes depends on sample thickness, mineral characteristics, and
the amount of light reaching the sample. Thus, any calibration of the temperature shift as a function of the
amount of light is complicated and, in most cases, impracticable. However, we demonstrate, based on cogen-
erated inclusions in opaque minerals and quartz that yield similar values during NIR microthermometry, that
for any mineral there is a range of light power and microscope settings for which no shift is noticeable within
the thermal-stage accuracy. These are defined as “ideal measuring conditions,” ensuring reliability of acquired
microthermometry data.

Introduction as a tool for the study of internal structures of NIR-transparent

The study of fluid inclusions (FIs) is an essential tool for
understanding crustal fluid processes (Roedder, 1972; Yardley
and Bodnar, 2014). Most studies are performed using clas-
sic transmitted-light microscopy. They are therefore limited
to transparent minerals and fail to provide information when
no suitable gangue minerals are present. In geologic environ-
ments where opaque minerals are abundant (e.g., ore deposits)
fluid inclusion studies rely on transparent minerals interpreted
on the basis of textural relationships to be cogenetic with the
opaque ore minerals. However, defining the temporal rela-
tionship between the FIs studied in gangue minerals and the
processes responsible for opaque mineral precipitation is chal-
lenging (Roedder and Bodnar, 1997; Wilkinson 2001).
Near-infrared (NIR) microscopy of opaque minerals has,
however, been successfully used to study crystallographic and
optical properties of minerals that are opaque to visible light,
such as pyrite, enargite, wolframite, hematite, and stibnite. The
first attempts were carried out in the first and middle part of the
last century (Lecomte, 1928; Bailly, 1938; Cervelle and Levy,
1971), but it was only with the pioneering work of Campbell
et al. (1984) that NIR microscopy experienced a breakthrough
†Corresponding author: e-mail, vcasanova@hotmail.fr
*Present address: CREAIT, CRC and CFI Services (CCCS), Memorial Uni-
versity of Newfoundland, St. John’s, Canada.
ISSN 0361-0128; doi: 10.5382/econgeo.2018.4616; 23 p.
Supplementary files available online, including Appendices 1–7.
minerals and soon after for fluid inclusion microthermometry
(Campbell and Robinson-Cook, 1987). Since then, most stud-
ies using NIR microthermometry on different NIR-transpar-
ent minerals have focused on ore deposit research (Mancano
and Campbell, 1995; Lüders, 1996, 2017; Lüders et al., 1999;
Lindaas et al., 2002; Kouzmanov et al., 2004, 2010; Rosiere and
Rios, 2006), but the method has also been successfully applied
to high-grade metamorphic minerals (Ni et al., 2008).
Several studies have shown that even intimately intergrown
opaque ore minerals and quartz may precipitate at different
stages and from different fluids (e.g., Campbell and Robin-
son-Cook, 1987; Campbell and Panter, 1990; Lüders, 1996;
Wilkinson et al., 2009; Kouzmanov et al., 2010; Wei et al.,
2012; Ortelli et al., 2015). This stresses the importance of
work on both opaque ore and transparent gangue minerals
and illustrates the relevance of NIR microthermometry.
However, NIR microthermometry suffers some technical
limitations. In the first paper suggesting the applicability of
NIR microscopy to fluid inclusion studies (Campbell et al.,
1984), it was recognized that NIR light interference with the
sample results in local heating of the sample and that cooling
of the sample during observation was necessary to prevent liq-
uid CO2 from homogenizing. Similarly, Lüders and Ziemann
(1999) observed heating of pyrite-hosted fluid inclusions (up to
about 35°C), caused by the IR light source during petrography
Submitted: September 26, 2017
1861 Accepted: October 9, 2018

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 1862
at room temperature. This problem does not arise in clas-
sic visible-light microthermometry because microscopes are
equipped, to protect the optical components, with a thermal-
reflection filter (TRF) that blocks wavelengths above 800 nm
at the exit of the light source—a filter that obviously has to
be removed to perform NIR microscopy. In order to assess
whether sample heating is inherent to NIR microscopy, sev-
eral studies performed microthermometry using a U.S. Geo-
logical Survey (USGS) gas-flow stage on inclusions hosted in
transparent minerals using both visible and NIR light (Camp-
bell and Robinson-Cook, 1987; Bailly et al., 2000; Lindaas et
al., 2002) and found no significant differences between the
two. However, Moritz (2006) pointed out that this exercise
was biased, because minerals transparent under visible light
require that measurements in NIR light are performed under
low-light intensity to avoid saturation of the camera detector.
In his study on enargite-hosted FIs, Moritz (2006) showed,
using a USGS gas-flow stage, that fluid salinities are overes-
timated (up to more than 100%) and that homogenization
temperatures are significantly underestimated due to shifts
in the recorded phase-transition temperature with increas-
ing NIR light intensity. Since then, only a few studies have
acknowledged this problem. Two studies did not notice any
significant shift in recorded ice-melting temperatures with
increasing light source intensity on rutile-hosted FIs (Zhu et
al., 2007) and on pyrite-hosted FIs (Zhu et al., 2013). In con-
trast, Kouzmanov et al. (2010) found that both enargite- and
pyrite-hosted fluid inclusion microthermometry was affected
by light source intensity. Similarly, Ortelli (2015) systemati-
cally documented significant shifts in recorded phase-change
temperatures of enargite-hosted fluid inclusion assemblages
with increasing light source intensity.
In the present work, we characterize significant light-
intensity-driven temperature shifts that are recorded in cer-
tain minerals, using samples containing fluid inclusions with
known salinities. The major goal of this work was to compre-
hend the physical processes responsible for sample heating
and to define experimental conditions under which results
obtained from NIR microthermometry are accurate. For
this purpose, we compared the effect of light source power
on microthermometry of synthetic fluid inclusions trapped in
quartz and in cogenetic opaque minerals.
Synthetic fluid inclusions were first commonly produced
with the method of Sterner and Bodnar (1984), in which
a piece of prefractured quartz is loaded into a noble metal
capsule together with a known solution and set at the cho-
sen pressure-temperature (P-T) conditions for the quartz to
seal. However, this method can produce erroneous results,
because the fluid inclusions may form before the experimen-
tal conditions or fluid-mineral equilibria are reached. For
this reason, Sterner (1992) developed an in situ quenching
method that allows the operator to choose the timing of frac-
turing and thus the timing of fluid inclusion formation. In this
method the quartz piece is loaded intact, and the fractures
are formed after some time of equilibration at experimental
conditions. For the present study, we used the in situ fractur-
ing method of Sterner (1992) to synthesize fluid inclusions in
a variety of sulfide minerals as well as hematite, wolframite,
and quartz. The experiments were designed such that in each
capsule fluid inclusions were synthesized simultaneously and
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CASANOVA ET AL.
from the same fluid in an opaque mineral and in quartz. This
procedure allows the comparison of microthermometry data
and fluid compositions from truly cogenetic fluid inclusions
hosted in quartz and an NIR-transparent mineral. To our
knowledge, this is the first synthetic fluid inclusion study in
opaque minerals, except for one study on sulfides (pyrite and
sphalerite) that was designed to provide material for decrep-
itometry experiments (Parilov et al., 1990) and not for micro-
thermometry, as in the present case.
Part I of the study of fluid inclusions in opaque minerals,
dealing with physical properties and the influence of trace ele-
ments on transmitted NIR light microscopy, is included in the
companion paper by Ortelli et al. (2018). In the first part of the
present study, we show how intrinsic parameters of the studied
minerals affect energy absorption and dissipation and how they
impact microthermometry. Using energy absorption and dissi-
pation physics in solids together with basic light source physics,
we define a set of parameters that can be modified to limit the
impact of the light source on microthermometry experiments.
In the second part, comparing LA-ICP-MS data of fluid inclu-
sions hosted in an opaque mineral and the associated quartz,
we demonstrate that fluids trapped in both minerals are similar
in composition and that, especially in the sulfide experiments,
significant amounts of gold from the capsule (up to 680 ppm)
can be solubilized and in some cases incorporated into the sul-
fide structure as a trace element or as nanoinclusions.
Basic Physics of Radiation, Absorption, and Diffusion
The main physical processes to consider when performing
NIR microthermometry experiments are radiative heating,
absorption, and thermal conduction. To a first approxima-
tion, three basic equations govern how much of the incident
energy reaching an object will be reflected, transmitted, or
absorbed. We show hereafter that in the case of a sample illu-
minated by a tungsten-halogen light source, when performing
NIR microthermometry most of the energy is absorbed in the
NIR region and converted to heat. This may lead to a signifi-
cant temperature difference between the illuminated part of
the sample and the thermocouple of the microthermometry
stage, which is itself protected from any interference with the
light and is, therefore, cooler. The basics of the processes gov-
erning this effect are covered here; further information can be
found in Zimmermann (2010) and Jun et al. (2010).
Light source physics
The common light source of optical microscopes is a tungsten
halogen lamp. It can be considered as a graybody and thus, its
radiant exitance, the radiant flux emitted per unit area (Ebλ(T,
λ), W.m–2), follows Planck’s law for a graybody (Nassau, 1983;
MacIsaac et al., 1999; Jun et al., 2010):
                        2⋅π⋅h⋅c 2
0 ⋅ε
Ebλ (T, λ) = —————————— , (1)
                    n ⋅λ ⋅[e 0
2 5 h⋅c /(n⋅λ⋅k⋅T) – 1]
where h is the Planck’s constant (6.62·10-34 J.s), c0 the speed
of light in vacuum (m.s–1), ε the emissivity of the graybody,
n the refractive index of the medium, λ the wavelength (m),
k the Boltzmann constant (1.38·10-23 J.K–1), and T the tem-
perature of the graybody (K). The temperature refers to the
tungsten filament.
 FLUID INCLUSION STUDIES IN OPAQUE ORE MINERALS: PART II 1863

The temperature of a graybody is linked to its exitance
Me (luminous flux per unit area, W.m-2), and to its radiated
power Pr (W), by the Stefan-Boltzmann law for a graybody
(MacIsaac et al., 1999):
                       P
Me = —r = ε⋅s⋅T4,
                       A
where A is the object surface area (m2), ε its emissivity, σ the
Stefan-Boltzmann constant (5.67·10–8 W.m–2.K–4), and T the
temperature of the graybody (K).
Absorption physics
When considering a light beam reaching a sample, part of this
light is reflected, and some is transmitted. The light that is nei-
ther transmitted nor reflected is absorbed. Here we neglect
scattering and luminescence that are orders of magnitude
lower than reflection, transmission, and absorption in NIR
microscopy. The intensity of light I(λ) transmitted through a
medium with thickness d (in cm) for a given wavelength (λ)
is described by the Lambert-Beer law (Zimmermann, 2010):
I(λ) = I0(λ)⋅e–α(λ)⋅d,
where I0(λ) is the light intensity entering the medium and is
a function of the light source, α(λ) the absorption coefficient
(cm–1), and d the thickness of the medium (cm). The absorp-
tion coefficient α(λ) is proportional to the extinction coeffi-
cient κ(λ) of the sample (Zimmermann, 2010):
                         4⋅π⋅κ
α(λ) = ———.
                            λ
The extinction coefficient together with the refractive
index define, for a given wavelength, how much of the light
is reflected, absorbed, and transmitted. As indicated by equa-
tion (3), the transmittance of a sample, defined by the fraction
of incident light transmitted through the medium, decreases
exponentially with the sample thickness. In semiconductors,
the case of most of the opaque minerals (Shuey, 1975),
absorbed energy in the NIR to mid-IR region is mostly due to
electronic transitions from the valence band to the conduction
band (Shuey, 1975). Electrons in a higher energy state will
dissipate this energy to return to the valence band through
(2) collision with random impurities and/or defects, transforming
this energy into heat (Shuey, 1975).
Energy dissipation
The energy accumulated as heat in a solid is dissipated via
conduction and through radiation. Radiation is governed by
the Stefan-Boltzmann law (eq. 2). Conduction of heat from
the hotter part to the cooler part of a solid obeys Fourier’s law,
which states that the heat flux is negatively proportional to the
temperature gradient (Kaviany, 2014):
q→ = –K(T)⋅∇T, (5)
where q stands for the heat flux (W⋅m–2), T for temperature
(K), and K(T) for the thermal conductivity of the sample
(W⋅m–1⋅K–1).
(3)
Sample Selection and Methods
Sample selection
Natural samples of pyrite, hematite, enargite, stibnite, wol-
framite, and Fe-rich and Fe-poor sphalerite were selected as
suitable host candidates for synthetic fluid inclusions, as they
(4) are often NIR transparent (Campbell, 1991) and commonly
encountered in various geologic environments. Although all
these minerals can be synthesized (Skinner and Barton, 1960;
Flanders and Remeika, 1965; Hsu, 1976; Schiek et al., 1990;
Seal et al., 1992, 1996), the crystals obtained are commonly
small in size. Natural samples with known compositional vari-
ations (Table 1) were selected based on their transparency to
NIR light and paucity in fluid inclusions. In this study, they

Table 1. List of Natural Samples Used for Synthetic Fluid Inclusion Experiments

Composition Trace element Trace element Zonation Origin

Mineral (wt %) [X] >10 ppm 10> [X] >1 ppm rating Analysis type (sample no.) Reference

Pyrite Fe (46.5), S (53.5) Se, Cu, Co, Zn, Ni Pb, Bi, Mo, As, 2 LA-ICP-MS Rosia Poieni, Kouzmanov
FeS2 Sn, Te, Sb, Ag, Au Romania (pyrite-1) et al., 2010
Enargite Cu (48.4), Sb, Bi, Fe, Zn, Se Ag, Sn, Cd, In, Te 3 LA-ICP-MS Butte, USA Ortelli, 2015
Cu3AsS4 As (18.3–20.1), (GRL-2810)
S (30.4–34.4)
Stibnite Sb (71.7), S (28.3) As, Ba, K N.A. 1 LA-ICP-MS Montauto, Italy This study
Sb2S3 (MA-01a) (Digital App. 1,
Table A1)
Wolframite W (60.0), O (20.8), Mg, Ti N.A. 3 EMPA San Cristobal, Peru Ortelli, 2015
(Fe,Mn)WO4 Fe (15.5–16.2), (FPE-4)
Mn (1.4–1.8)
Sphalerite Zn (66.6), S (33.4) Fe, Cd, Mn, Cu, In Co, Ga, As, Ag 2 LA-ICP-MS Butte, USA Ortelli, 2015
(Fe-poor) (GRL-2958)
Sphalerite Zn (55.1–65.8), Cd, Mn, Cu N.A. 2 EMPA Morococha, Peru This study
(Fe-rich) Fe (1.4–9), S (33.0) (KMO-006) (Digital App. 1,
Table A2)
Hematite Fe (69.4), O (30.6) Al, Cu, Ni, Zn, N.A. 3 EMPA Rio Marina, Elba Dünkel, 2002
Fe2O3 Mg, Si, Mn

Notes: Presence of mineral zoning is assessed on a 1 to 3 level basis: 1 = no zonation, 2 = a few large-scale growth zones, 3 = intensely zoned
Abbreviations: EMPA = electron microprobe analysis, LA-ICP-MS = laser ablation-inductively coupled plasma-mass spectrometry, N.A. = not analyzed

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 1864 CASANOVA ET AL.

will be referred to as the opaque minerals. Their origin and
composition as well as references for detailed information
about their provenance are summarized in Table 1.
Synthetic fluid inclusions: experimental protocol
The experiments were carried out at the Bavarian Geoinsti-
tute, Bayreuth, Germany. Each opaque mineral sample was
prepared as a centimeter-long cylinder (ø ≈ 3.5 mm) and
loaded into a gold capsule together with about half of its
weight in powdered form (63–125 µm grain fraction) plus a
similar-sized cylinder of synthetic quartz (Fig. 1). Addition-
ally, 30 µL of a solution with one of the following compositions
(Table 2) was added:
1. H2O + 5 wt % NaCl equiv, spiked with 498 ppm Cs
2. H2O + 10 wt % NaCl equiv, spiked with 494 ppm Cs
The mineral powder was added in order to maximize the
amount of mineral surface in contact with the fluid so that
fluid-mineral equilibrium would be reached faster. After clos-
ing by arc welding, the capsule was shrunk in an autoclave
by a rapid pressure increase to 2 kbar at room temperature.
Comparison of the capsule weight before and after shrink-
ing was used to check for any leakage. The capsule was then
loaded into a rapid-quench, cold-seal pressure vessel similar
to the one described in Matthews et al. (2003). The setup
at the Bavarian Geoinstitute, where experiments were per-
formed, uses water as a pressure medium, and the capsule
holder is maintained at the hot end of the autoclave using a
magnet. In order to obtain useful fluid inclusions, it is neces-
sary to use high temperatures. We thus chose experimental
temperatures such that they were close to the stability limit of

Equilibration In situ fracturing Healing

(2-7 days) (7-15 days)

Au capsule
+
Opaque min. powder
Quartz +
known solution 1 or 2

opaque

P = 2 kbar P = 2 kbar P = 2 kbar

T = 500-700 °C rapid drop to room T T : idem equilibration
Fig. 1. Schematic protocol used to cosynthesize fluid inclusions in an opaque mineral (min.) and a synthetic quartz. A gold
capsule is loaded with an opaque mineral cylinder (approximately 3.5 mm in diam, 10 mm long), about half its powdered
weight equivalent, and a synthetic quartz cylinder with similar dimensions; 0.3 µL of one of the two starting solutions is added
(solution 1 = 10 wt % NaCl equiv + 494 ppm Cs; solution 2 = 5 wt % NaCl equiv + 498 ppm Cs). Temperature of the experi-
ment, equilibration time, and healing period are set individually for each mineral (see Table 2 for experiment conditions).

Table 2. Experimental Conditions for Synthetic Fluid Inclusion Runs

Min. Au In situ Total capsule

Min. powder Qtz capsule Solution cracking Total after
Sample T P NaCl Cs weight weight weight weight weight Run after capsule experiment
(°C) (kbar) (wt %) (ppm) (mg) (mg) (mg) (mg) (mg) (days) (days) (mg) (mg)

Enargite-1 620 2 10 494 239 170 110 1,208 29  9 2 1,757 1,757

Enargite-2 620 2  5 498 321 157 117 1,284 29  8 2 1,909 1,909
Pyrite-1 700 2 10 494 312 145 126 1,237 30  9 2 1,847 1,847
Pyrite-2 700 2  5 498 334 172 126 1,264 30  8 2 1,926 1,926
Hematite-1 650 2 10 494 318 206 115 1,249 30  9 2 1,918 1,918
Hematite-2 580 2 10 494 422 189 125 1,246 30  8 2 2,012 2,007
Fe-poor Sl-1 700 2 10 494 276 138 119 1,233 31  9 2 1,796 1,796
Fe-poor Sl-2 700 2  5 498 253 180 122 1,254 30  9 2 1,839 1,839
Fe-rich Sl 650 2  5 498 251 156 118 1,278 30  8 2 1,833 1,833
Wolframite 700 2 10 494 352 175 118 1,250 31  9 2 1,925 1,925
Stibnite 500 2 10 494 165 144 114 1,254 30 21 7 1,707 1,699

See text for discussion of the parameters

Abbreviations: Min. = mineral, Qtz = quartz, Sl = sphalerite

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by Univ de Geneve UNIGE-Biblio SC Terre Enviornment, Kalin I. Kouzmanov
 FLUID INCLUSION STUDIES IN OPAQUE ORE MINERALS: PART II
the target mineral but not higher than 700°C. The pyrite, Fe-
poor sphalerite, and wolframite experiments were conducted
at 700°C. Enargite runs were conducted at 650°C because
enargite melts above 670°C (Maske and Skinner, 1971; Seal et
al., 1996). The hematite runs were conducted first at 650°C to
remain below the hematite-magnetite transition temperature,
according to Tareen and Krishnamurthy (1981), and in a sec-
ond attempt at 580°C to remain below the Curie temperature
of magnetite that may trigger the reduction of hematite to mag-
netite (Chakraborty, 1999) and render the sample opaque to
NIR light. The stibnite experiment was carried out at 500°C
in order to remain below the decomposition temperature of
556°C (Seal et al., 1992). Experimental conditions are summa-
rized in Table 2. For each run, the pressure was set to 2 kbar
and the temperature raised isobarically to the experiment tem-
perature (Table 2) in order to remain in the one-phase field of
the H2O-NaCl system (Driesner and Heinrich, 2007). Samples
were left for two days at these P-T conditions to let the fluid
equilibrate with the minerals before entrapment. An exception
was stibnite, which was allowed to equilibrate for seven days
due to the lower experiment temperature. The capsule was
then quenched by dropping it within 1 s to the cold end of the
autoclave using the magnet. As a result of thermal contraction,
fractures were created (Fig. 1). The capsule was then rapidly
moved back to the hot end of the autoclave where it was kept at
constant P-T conditions for another seven days (stibnite for 14
days) for the cracks to seal and fluid inclusions to form. Finally,
the capsule was cooled along an isochoric path defined by the
pressure vessel to room temperature in about 40 min.
The recovered opaque minerals and quartz were impreg-
nated in special epoxy that is heat resistant up to 350°C (EPO-
TEK 353ND) and were prepared as doubly polished sections
with a thickness of 150 to 500 µm.
NIR microscopy
Petrography was performed using an Olympus BX51 micro-
scope equipped with Olympus IR objectives at the Depart-
ment of Earth Sciences, University of Geneva, Switzerland.
The microscope was modified to accept a removable thermal-
reflection filter (Olympus 45SCF) placed at the exit of the light
source. The light source was a standard 100-W microscope
lamp (Osram HLX-64625). The microscope is equipped with
an Olympus U-LWCD condenser that has a condenser dia-
phragm (graduated numerical aperture 0.05–0.65). Situated
on the light beam trajectory between the source and the con-
denser is a field diaphragm on top of which an IR polarizer
(Olympus U-POTIR) can be placed. The field diaphragm aper-
ture can be modified and is graduated between 0% (closed)
and 100% (fully open). A schematic diagram of the microscope
setting with emphasis on the light beam trajectory between the
source and the sample is illustrated in Figure 2. The 100-W
lamp intensity is controlled by an Olympus TH4-200 external
controller and monitored by a voltmeter mounted in parallel.
The electric current delivered by the external controller was
measured together with the voltage, allowing us to calculate the
power delivered to the lamp. Near infrared observations and
image acquisitions were done through the CellP software con-
nected to either one of our NIR cameras: Olympus XM10 or
Hamamatsu C2400-03d with working spectral ranges of 0.4 to
1.1 µm (Olympus technical documentation) and 0.4 to 2.2 µm
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by Univ de Geneve UNIGE-Biblio SC Terre Enviornment, Kalin I. Kouzmanov
1865
(Hamamatsu technical documentation), respectively (more
information can be found in Ortelli et al., 2018).
Fourier transform infrared (FTIR) spectroscopy
Fourier transform infrared (FTIR) transmission and reflec-
tion spectra of an area of about 30 × 30 µm for each min-
eral over zones of interest, as well as transmission spectra for
the heat-reflection filter and the polarizer, were acquired at
the Department of Quantum Matter Physics, University of
Geneva, on a Bruker Vertex 70v spectrometer coupled to a
Bruker Hyperion 2000 microscope at room temperature.
The spectrometer was optimized for NIR conditions using a
quartz-tungsten-halogen light source and a CaF2 beam split-
ter. Spectral resolution was set to 10 cm–1 for all minerals.
Spectra presented are cut at 0.8 µm and remain noisy up to
1 µm as the detection limit of the NIR detector is reached
(Ortelli et al., 2018). Absorption spectra are obtained by sub-
tracting from 100 the sum of the reflection and transmission.
Radiant exitance measurements
Radiant exitance of the 100-W tungsten-halogen lamp (Osram
HLX 64625) used for our microthermometry experiments was
acquired between 900 and 2,300 nm using an Andor Sham-
rock 500i monochromator equipped with a strained InGaAs
detector. It was calibrated using a 2,700-K tungsten-halogen
reference source (Ocean Optics).
Microthermometry
Microthermometry was performed using a Linkam FTIR-
600 stage, equipped with sapphire windows and controlled
IR Camera
Heating-freezing stage
Sample
Condenser lens
Condenser diaph.
Thermal-reflection
Field diaph. filter
Light source
(100 W tungsten-halogen)
Field lens Collector
Light source
lens
controller
V Voltmeter
Fig. 2. Schematic of the light beam trajectory between the source and the
sample. Light source intensity is externally controlled and monitered by a
voltmeter. When the removable thermal-reflection filter is in place, only
wavelengths below 1,100 nm are transmitted. Field and condenser dia-
phragms (diaph.) control the amount of light effectively reaching the sample.
IR = infrared.
 1866
by the Linksys 32X software at the Department of Earth Sci-
ences, University of Geneva (more details about the analytical
setup can be found in Ortelli et al., 2018). The stage was cali-
brated using SYNFLINC synthetic fluid inclusions standards
in quartz (Sterner and Bodnar, 1984) at –56.6°, 0.0°, and
374.1°C. Final ice-melting temperatures (Tmice) of selected
fluid inclusions were recorded under various light source
operating power and microscope settings to produce devia-
tion curves. The microscope settings in this study refer to all
the objects situated on the light beam trajectory between the
light source and the sample, which can be modified by the
user. Microscope settings therefore encompass both field and
condenser diaphragms, the IR polarizer, and the removable
thermal-reflection filter (Fig. 2). A deviation curve for a given
microscope setting is the plot of the recorded phase-change
temperatures as a function of the light source operating power.
The true Tmice was measured by adapting the cycling method
commonly used in microthermometric studies (Goldstein and
Reynolds, 1994), with the light source switched off during the
heating run. “Ideal measuring conditions” refer in this study
to the range of light source intensities and microscope set-
tings under which the recorded Tmice of a fluid inclusion is the
same as its true ice-melting temperature. In enargite-2, for
one microscope setting only, freezing temperature (Tfreeze) and
final clathrate-melting temperature (Tmclath) were recorded in
addition to the Tmice. The freezing temperature corresponds
to that at which ice nucleation occurs (Goldstein and Reyn-
olds, 1994), while Tmclath corresponds to the temperature at
which final melting of the gas-hydrate solid phase is observed.
Laser ablation-inductively coupled plasma-mass
spectrometry (LA-ICP-MS)
Fluid inclusion compositions in the opaque minerals and
their associated quartz were analyzed using the laser ablation-
inductively coupled plasma-mass spectrometry (LA-ICP-MS)
facility at the Institute of Geochemistry and Petrology, ETH
Zurich, Switzerland. Ablation was performed in a home-
made glass ablation cell, using a homogenized ArF excimer
laser (193 nm) coupled to an ELAN 6100 DRC ICP quad-
rupole mass spectrometer (Günther et al., 1997; Heinrich et
al., 2003). The thermal-reflection filter of the Zeiss micro-
scope belonging to the LA-ICP-MS system was removed.
The Olympus XM10 camera was mounted on the microscope
to facilitate work in opaque minerals, except for pyrite and
hematite, which remained opaque with this hardware. Abla-
tion of pyrite-hosted fluid inclusions was performed using the
method described by Kouzmanov et al. (2010), using reflected-
light reference images combined with NIR transmitted-light
images acquired with the Hamamatsu camera during fluid
inclusion petrography. Because hematite remained opaque
to both NIR cameras used, fluid inclusions were analyzed
through blind shooting, using a 40-µm ablation diameter, in
the trails left on the section surface by fluid inclusion opening
during polishing. The crater diameter during quartz ablation
was progressively adjusted using an iris diaphragm to reduce
risks of crack formation and inclusion decrepitation (Guillong
and Heinrich, 2007). In opaque minerals, ablation was per-
formed with constant pit diameter between 20 and 60 µm, so
that the pit was larger than the fluid inclusion to ensure com-
plete ablation. Ablation and ICP-MS parameters are reported
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CASANOVA ET AL.
in Digital Appendix 2. Data reduction was performed using
the SILLS software (Guillong et al., 2008a). Cesium was used
as an internal standard, and all analyses were matrix corrected.
The matrix (i.e., host) correction in SILLS is done by getting
the matrix composition before and after the fluid inclusion,
if possible. The average of this composition is assumed to be
present in the matrix around the inclusion, i.e., the part of the
host ablated at the same time as the inclusion. Using a major
component of the matrix, e.g., Si for quartz or Cu for enar-
gite, as a matrix tracer, meaning the contribution from the
inclusion to the measured signal of that element is negligible,
the matrix contribution of the other elements to the inclusion
signal is calculated and subtracted from the combined signal
to get the net inclusion signal using the following equation
(Guillong et al., 2008b):
                 IMT Host (
IE Incl. = IE Mix –   IE Host
——— )
× IMT mix , (6)
where IE is the intensity of analyzed element, IMT is the inten-
sity of matrix tracing element, Host refers to the pure host
signal, mix to the inclusion and host signal received during the
ablation of the inclusion, and Incl. to the calculated inclusion
signal.
Only signals from elements that are clearly present (by
visual inspection of the plotted inclusion signal) were consid-
ered as valid analyses. The rest were marked as not quanti-
fiable. Analyses where partial decrepitation occurred during
ablation, where fluid inclusions could not be individualized
due to overlapping signals, or where the signal could not be
fully recorded because integration times that were too short
were discarded.
Results
Physical properties of the microscope components
The measured NIR exitance of the light source used for our
microthermometry experiments when operated at 100 W is
presented in Figure 3A. Its exitance fits that of a graybody
(see the “Light source physics” section) at a temperature of
2,910 K and an emissivity of 0.386. This latter value equals
the one calculated by MacIsaac et al. (1999) for a tungsten
filament in a glass envelope. Figure 3A shows that most of the
light emitted by a classic microscope lamp is emitted in the
NIR region between 780 and 3,500 nm. For this reason, all
subsequent transmission and absorption spectra will be pre-
sented up to a wavelength of 3,500 nm.
Using equation (2) it is possible to calculate the filament
temperature of the light source at any operating power (Table
3). The light source emitted radiation has been calculated for
different operating powers using Planck’s law for graybodies
(eq. 1; Fig. 4A). Integrations of equation (1) over selected
ranges and comparisons with the total exitance are presented
in Table 3. Selected spectral ranges correspond to the ones
that would be obtained by removing all filters and placing
at the exit of the light source a thermal-reflection filter with
a cutoff fitting the upper spectral limit of the camera used
(Olympus XM10: 1,100 nm; Hamamatsu: 2,200 nm). Results
obtained in the visible region correspond to classic micro-
thermometry and are given for reference. When increasing
the light source power, not only does the exitance increase
 FLUID INCLUSION STUDIES IN OPAQUE ORE MINERALS: PART II 1867

E (105 W.cm-3) T (%) T (%)

12.5 100
Olympus XM10 100

A Olympus XM10
Hamamatsu C2400-03d
B
10 80 80

Hamamatsu C2400-03d

7.5 60 60

5 40 40

2.5 20 20

0
0 500 1000 1500 2000 2500 λ (nm)
3000 500 1000 1500 2000 2500 3000 λ (nm)
Radiant exitance (10 W.cm ) 5 -3 Transmittance T(%) Enargite 1 Pyrite Stibnite Wolframite Z1
100W lamp Polarizer Enargite 2 Fe-poor Sphalerite 1 Wolframite Z2
Graybody 2910 K, ε=0.386 Thermal-reflection filter

Fig. 3. (A) 100-W lamp radiant exitance (E, in 105 W.cm–3) and near-infrared (NIR) transmittance (T, in %) of the thermal-
reflection filter and polarizer. The lamp radiant exitance can be approximated by a graybody at a temperature of 2,910 K and
having an emissivity (ε) of 0.386. (B) NIR transmittance as a function of wavelength (λ, in nm) of a 30- × 30-µm area over the
studied fluid inclusion in different host minerals. Dashed vertical lines represent upper spectral limits of the two NIR cameras
used (Olympus XM-10 and Hamamatsu C2400-03d).

with the filament temperature, but so does the percentage of
light emitted within a selected range (Table 3). This is con-
sistent with Wien’s displacement law, which states that the
peak emission wavelength shifts toward shorter wavelengths
as the temperature of the object rises (Jun et al., 2010; see
Fig. 4A). Consequently, there is no linear correlation between
the radiant flux in a selected range and the light source power
(Fig. 4B). The FTIR transmission spectrum acquired on the
thermal-reflection filter (Fig. 3A) shows that transmissivity is
around 80% to 90% below 1,020 nm and rapidly decreases
above this to reach <10% from 1,100 nm upward. The FTIR
spectrum acquired on the IR polarizer (Fig. 3A) shows a slight
increase in the transmissivity from 10% at 800 nm to 40%
between 2,000 and 2,700 nm. Besides polarizing the light, it
also strongly reduces the amount of light reaching the sample,
especially in the shorter wavelengths.

Table 3. Calculated Radiant Flux and Percentages of Light Emitted in Selected Ranges for Different Light Power

Light source Visible Thermal-reflection filter Hamamatsu camera

(380–720 nm) (0–1,100 nm) (0–2,200 nm)

T filament Exitance Exitance Radiant flux Exitance Radiant flux Exitance Radiant flux
V Power (W) (K) (W.cm–2) (%) (W.cm–2) (%) (W.cm–2) (%) (W.cm–2)

1   2.4 1,141   4 0.0 1.E-04  0.3 1.E-2 16.6   0.6

2   6.5 1,472  10 0.1 7.E-03  2.2  0.2 32.9   3.4
3  12.1 1,718  19 0.3 6.E-02  5.3  1.0 44.2   8.4
4  18.6 1,912  29 0.8  0.2  8.7  2.5 52.0  15.2
5  26.4 2,085  41 1.4  0.6 12.3  5.1 58.0  24.0
6  34.9 2,237  55 2.2  1.2 15.8  8.6 62.6  34.3
7  44.3 2,374  69 3.2  2.2 19.1 13.3 66.3  46.1
8  54.5 2,500  85 4.2  3.6 22.2 19.0 69.3  59.3
9  65.2 2,614 102 5.3  5.4 25.1 25.7 71.8  73.4
10  76.8 2,724 121 6.4  7.7 27.8 33.6 73.9  89.1
11   89.1 2,827 140 7.6 10.6 30.4 42.5 75.7 105.9
12 100.0 2,910 157 8.6 13.5 32.5 50.9 77.1 121.0
12.5 108.8 2,972 171 9.4 16.0 34.0 58.0 78.1 133.2

Notes: Electromagnetic ranges chosen to compare (1) classical microthermometry (visible light), (2) near-infrared microthermometry restricted to the Olym-
pus XM10 camera capacities, (3) near-infrared microthermometry restricted to the Hamamatsu camera capacities; calculations have been done using
Plank’s law for the emissive power distribution and the Stefan-Boltzmann law for the total radiant flux

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 1868 CASANOVA ET AL.

P=109 W - T=2970 K - 12.5 V 140 0-2200 nm

A P=100W - T=2910 K - 12 V
B
120
10
Radiant exitance (105 W.cm-3)

Radiant flux (W.cm-2)

P=89 W - T=2827 K - 11 V
100
8
P=77 W - T=2723 K - 10 V
80
P=65 W - T=2614 K - 9 V
6 0-1100 nm
60
P=55 W - T=2500 K - 8 V

4 P=44 W - T=2373 K - 7 V 40

P=26 W - T=2084 K - 5 V 20
2
P=12 W - T=1717 K - 3 V
P=2.4 W - T=1720 K - 1 V 0 20 40 60 80 100 120
0 500 1000 1500 2000 2500 3000 λ (nm) Light source power (W)
Fig. 4. (A) Radiant exitance curves of our light source approximated by a graybody emissivity (ε) of 0.386 operated at different
powers. Following Wien’s displacement law, the locus of the peak shifts toward shorter wavelengths with increasing filament
temperature. (B) Calculated radiant flux emitted by the tungsten-halogen light source as a function of its operating power
for two selected spectral ranges. The spectral range can be adjusted by placing a thermal-reflection filter of a chosen cutoff
at the exit of the light source.

Synthetic fluid inclusion microthermometry
Quartz: As we expected from previous experiments (e.g.,
Sterner, 1992), fluid inclusions created in the synthetic quartz
samples in the lowest temperature experiments (≤600°C)
were scarce, small (5–15 µm), and scattered in a few cracks.
With increasing experiment temperature, fluid inclusion den-
sity distribution, size (up to 100 µm), as well as the number
of cracks increased (Fig. 5E). In the quartz included with the
enargite experiments and the pyrite-1 experiment, a transpar-
ent solid inclusion could be observed in most FIs. In both
quartz samples included with the pyrite experiments, a very
small opaque solid was observed in some of the FIs. The
transparent inclusion was unstable under the Raman laser
beam but could be successfully identified as native sulfur,
whereas the opaque inclusions were identified as small pyrite
crystals using Raman spectrometry. No solid inclusions were
observed in the quartz-hosted FIs associated with the other
experiments. Table 4 reports the Tmice of the quartz-hosted
inclusions included in each autoclave experiment. Each value
is averaged over a population varying between seven and 31
fluid inclusions. For most experiments, the standard deviation
of Tmice data is below the Linkam stage precision (0.1°C), the

Table 4. Average Ice-Melting Temperature (Tmice) and Standard Deviation (1σ) of a Fluid Inclusion Population
Measured in Quartz and in Opaque Minerals Under Ideal Measuring Conditions

Salinity Average No. of fluid Daughter

Experiment (wt % NaCl equiv) T exp. (°C) Host Tmice (°C) 1σ inclusion mineral

Enargite-1 10 620 Quartz –7.6 0.18 12 S

Enargite –7.6 0.07  7 S
Enargite-2  5 620 Quartz –3.0 0.05  8 S
Enargite –3.0 0.05  6 S
Pyrite-1 10 700 Quartz –7.9 0.15 31 Py-S
Pyrite n.m. - - -
Pyrite-2  5 700 Quartz –3.9 0.09  7 Py
Pyrite n.m. - - -
Fe-poor sphalerite-1 10 700 Quartz –7.6 0.14 15 No
Fe-poor sphalerite –7.6 0.05   4 No
Fe-poor sphalerite-2   5 700 Quartz –3.9 0.06 12 No
Fe-poor sphalerite n.m. - - No
Fe-rich sphalerite  5 650 Quartz –4.0 0.04  7 No
Fe-rich Sphalerite n.m. - - No
Stibnite 10 500 Quartz –7.2 0.04  9 No
Stibnite –7.2 0.06  7 No
Hematite-1 10 650 Quartz –7.4 0.07  7 No
Hematite n.m. - - -
Hematite-2 10 580 Quartz –6.1 0.06 16 No
Hematite n.m. - - -
Wolframite 10 700 Quartz –7.8 0.06 30 No
Wolframite –7.8 0.06  8 No

Notes: Expected ice-melting temperatures for solutions at 5 and 10 wt % NaCl equiv are –3° and –6°C, respectively; solid inclusions have been observed in
fluid inclusions hosted in the quartz from the pyrite and enargite experiments; native sulfur (S) and pyrite (Py) daughter minerals are observed in certain
fluid inclusions; - = no data, exp. = experiment, n.m. = not measurable

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 FLUID INCLUSION STUDIES IN OPAQUE ORE MINERALS: PART II 1869

A Stibnite

1 mm

10 µm

B Wolframite
1 mm
Z1

Z2

20 µm

C Enargite

1 mm
20 µm

D Fe-poor sphalerite
50 µm

1 mm

E Quartz associated with Fe-poor sphalerite 1

50 µm
1 mm

Fig. 5. (A-E) Photo-stitched panoramas of 150-µm-thick sections from recovered samples from the autoclave experiments
and studied fluid inclusions. Stibnite, wolframite, and enargite pictures were taken with our near-infrared (NIR) camera
(Olympus XM10), while Fe-poor sphalerite and quartz were taken with a classic visible-range camera. Red squares indicate
the location of acquired transmittance and reflectance Fourier transform infrared spectra presented in this study.

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 1870 CASANOVA ET AL.

two exceptions being the quartz associated with the enargite-1
and pyrite-1 experiments, which have standard deviation up to
0.18°C. Only very small deviations from the true Tmice were
recorded when increasing the light source intensity and open-
ing diaphragms. The maximum recorded shift was –0.2°C at
the highest light power, diaphragms fully open and all filters
removed.
Wolframite: In wolframite, primary internal textures
were preserved after the autoclave experiments (Fig. 5B)
and several cracks with secondary fluid inclusions were cre-
ated. Unfortunately, most of these fluid inclusions remained
opaque due to internal reflections. Microthermometry could
be performed only on a few small (3–7 µm in size) fluid inclu-
sions. The average Tmice obtained on eight fluid inclusions
under ideal measuring conditions (as defined in the “Micro-
thermometry” section) was –7.8°C. Numerous natural fluid
inclusions were preserved during the autoclave experiment.
These are bigger (up to 50 µm), most are transparent, and
they are generally more suitable for microthermometry. They
yielded Tmice between –2.8° and –4.6°C. In the wolframite
slab shown in Figure 5B, fluid inclusion FI1 was selected in
the bright zone Z1 and fluid inclusion FI2 in the dark zone Z2.
Both yielded similar Tmice (–4.4°C) under ideal measuring
conditions. The absorption spectra obtained for both zones
(Fig. 6) are very similar in the NIR region except between 800
and 1,200 nm, where the darker area (Z2) has an absorption
of 75% in contrast to 40% at around 1,000 nm in the bright
zone 1.
In the bright zone 1, Tmice for different microscope settings
and light source powers were recorded on FI1 (Fig. 7). When
both diaphragms were nearly closed and the 1,200-nm ther-
mal-reflection filter was inserted, the lowest Tmice recorded
(–4.5°C) was close to the true temperature (–4.4°C; measured
with the cycling method with the light source partly switched
off). For all the other microscope settings, the recorded Tmice
decreased with increasing light source power. The lowest
Tmice (–59.5°C) was obtained when maximizing the amount
of light reaching the sample by fully opening the diaphragms,
removing the thermal-reflection filter, and operating the light
source at its maximum (108 W). With these microscope set-
tings and the light source voltage set to 2 V (6.5 W), Tmice
was already underestimated by 25% (–5.5°C). With both dia-
phragms fully open and the thermal-reflection filter and the
polarizer mounted, Tmice recorded on FI1 was –7.1°C, and it
was –23.8°C when the polarizer was removed (Fig. 7). For any
given microscope setting, Tmice follows a third-order polyno-
mial trend with the light source power. Figure 8A compares
recorded Tmice for FI1 and FI2 using three different micro-
scope settings. When both diaphragms were nearly closed, no
effect of increasing light intensity was observed on either FI.
Upon opening the diaphragms, the deviations recorded in the
inclusion (FI2) in the dark zone are larger than those for FI1
in the bright zone for the same setting. Keeping the thermal-
reflection filter in place, the lowest Tmice for FI2 was twice
as low as that for FI1 (Tmice = –44.2°C at 108 W for FI2 vs.
–23.8°C for FI1).
For both fluid inclusions FI1 and FI2, for most microscope
settings, the light source power has an important impact on
the measured Tmice when operated at 50 W and above (Fig.
8). For all other opaque minerals in this study, Tmice as a func-
tion of light power is reported only in the range of 0 to 50 W
and under five different microscope settings. For all of them,
the diagrams covering the full 100-W lamp power range are
available in Digital Appendix 3, and values are reported in
Digital Appendix 4.
Enargite: Two enargite autoclave experiments, labeled
enargite-1 and enargite-2, were conducted under the same
P-T conditions but with the two different aqueous solu-
tions described above containing 10 and 5 wt % NaCl equiv,
respectively (Table 2). In both experiments, primary inter-
nal structures of enargite crystals were preserved (Fig. 5C),
except for certain sealed cracks that show an enhanced

Olympus XM10 limit

100
Thermal-reflection filter Hamamatsu C2400-03d limit

80
Absorption (%)

60

40

20

0
800 1000 1500 2000 2500 3000 λ (nm)
Quartz Fe-poor Sphalerite 1 Pyrite Stibnite Enargite 1 Enargite 2 Wolframite Z1 Wolframite Z2

Fig. 6. Absorption of a 30- × 30-µm zone over studied fluid inclusions of different near-infrared (NIR)-transparent miner-
als. Absorption was obtained by subtracting from 100 the Fourier transform infrared (FTIR) reflectance and transmittance
spectra. Absorption of quartz is given for comparison but was acquired on a 500-µm-thick sample instead of 150 µm for the
others. Vertical gray and red dashed lines correspond to the upper spectral limit of the two cameras used (Olympus XM-10
and Hamamatsu 2400-03d) and the thermal-reflection filter cutoff, respectively. Regular high-frequency oscillations observed
on the different spectra are Fabry-Perot interferences due to multiple internal reflections at the mineral-air interfaces.

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 FLUID INCLUSION STUDIES IN OPAQUE ORE MINERALS: PART II 1871

Lamp power (W)

0 20 40 60 80 100 120

-10
Diaphragm settings
Symbol Filters
Field Condenser
≈0% 0.1 TRF
-20
10% 0.3 TRF
TRF
100% 0.65
Tmice (°C)

Pol.
-30 10% 0.65 TRF
50% 0.3 TRF
100% 0.3 TRF
-40 50% 0.65 TRF
100% 0.65 TRF
50% 0.3 None
-50 100% 0.65 None

-60

Fig. 7. Effect of light power (W) on recorded final ice-melting temperature (Tmice) of fluid inclusion 1 in wolframite (zone
1) with different field (0% = nearly closed, 100% = fully open) and condenser (0.05 = minimum opening, 0.65 = maximum
opening) diaphragm openings. Abbreviations: Pol. = polarizer, TRF = thermal-reflection filter.

transparency relative to their surroundings. In both experi-
ments, several cracks were created containing fluid inclusions
ranging in size from a few microns up to 30 µm. In experiment
enargite-2, fewer fluid inclusions were suitable for microther-
mometry than in enargite-1, as many are opaque due to inter-
nal reflections. Ice-melting temperatures recorded under
ideal measuring conditions were similar to those obtained
from quartz-hosted fluid inclusions, giving an average Tmice
of –7.6°C in enargite-1 (n = 7) and –3°C in enargite-2 (n =
6) (Table 4). In all these inclusions, a solid daughter phase
can be observed, generally hidden beneath the vapor bubble.
During both microthermometry experiments enargite-1 and

A Lamp power (W) B FI 1

0 20 40 60 80 100
6 W-2 ms 35 W-20 ms

-10

20 μm
Tmice (°C)

-20

FI 2
35 W-250 ms 55 W-220 ms
-30

FI Diaphragm settings
-40 Filter
1 2 Field Condenser
≈0% 0.1 TRF
50% 0.3 TRF 20 μm
100% 0.65 TRF
-50
Fig. 8. (A) Comparison of the effect of light power on recorded ice-melting temperature (Tmice) of two fluid inclusions, FI1
and FI2, located in areas with contrasting absorption in wolframite with three different microscope settings. FI1 and FI2
have the same true Tmice. (B) Near infrared photomicrographs of FI1 and FI2 with two microscope settings. For each the
light source operating power (W) and required camera acquisition time (ms) to perform microthermometry are reported.
Abbreviation: TRF = thermal-reflection filter.

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 1872
enargite-2, a gas-hydrate clathrate phase was observed. In
both experiments, natural fluid inclusions were also preserved
as attested by their Tmice (–1.8° to –2.4°C), similar to those
found in parts of the same sample that did not undergo auto-
clave experiments (Ortelli, 2015). These natural fluid inclu-
sions contain neither solid daughter phases nor gas-hydrate
clathrates.
Fourier transform infrared spectroscopy curves show that
absorption can vary significantly within a single crystal (Digital
App. 5). A fluid inclusion from each experiment was chosen
in zones with contrasting absorption patterns (Fig. 6). In both
experiments the impact of light intensity was negligible when
both diaphragms were nearly closed. Similar to wolframite,
Tmice recorded on both fluid inclusions was strongly affected
by the light source intensity. The deviation curves obtained
are more prominent in the more absorbing enargite-1 (Fig. 9),
where the lowest Tmice recorded was –100°C (Digital App. 4).
For the FI from enargite-2, three phase-change temperatures
(freezing, ice-melting, and clathrate-melting temperatures)
were recorded with the field diaphragm and condenser dia-
phragm aperture set to 50% and 0.3, respectively (Fig. 10A;
Table 5). The shifts from the true temperatures are shown
in Figure 10B. Although each measurement can be repro-
duced, phase-change temperature shift curves do not overlap.
All three deviation curves exhibit a similar shape, but their
slopes are different. There is no simple correlation between
the true temperature and the slope of the deviation curve,
as evidenced by the fact that Tmclath, the highest of the three
temperatures, has its shift curve between the two others. In
addition, tests were carried out aiming to characterize phase-
change response time upon changing microscope settings or
light intensity. This was done by cooling the stage tempera-
ture 0.1°C to up to 20°C below the freezing temperature
of the inclusion while the light source was operated at high
power (>50 W). Under these conditions, a sudden closure of
one of the diaphragms or an important decrease of the light
source intensity immediately resulted in the freezing of the
fluid inclusion.
Table 5. Recorded Phase-Change Temperatures at Different Light Source
Intensities Obtained on a Fluid Inclusion Hosted in Enargite 2
Light
Tmice (°C) Tmclath (°C) Tfreeze (°C) voltage (V)
–3.0 13.8 –41.5  0.00   0.0
–3.0 13.8 –41.5  1.00   2.3
–3.0 13.7 –41.9  2.02   6.6
–3.3 13.4 –42.4  3.01  12.1
–3.7 12.7 –43.0  4.02  18.8
–4.3 11.8 –44.0  5.04  26.7
–5.2 10.6 –45.3  6.00  34.9
–6.3  9.1 –47.2  6.98  44.1
–7.6  7.4 –49.4  8.02  54.7
–9.2  5.3 –51.7  8.95  64.8
–11.2  3.1 –54.2 10.05  77.6
–13.3  0.8 –57.5 10.99  89.2
–15.5 n.a. –61.4 11.97 101.9
–16.7 –3.4 –62.3 12.48 108.9
Notes: Microscope settings remain unchanged: thermal-reflection filter is in,
field and condenser diaphragm apertures are 50% and 0.3, respectively
Abbreviations: n.a. = not analyzed, Tfreeze = temperature of freezing, Tmclath =
final clathrate-melting temperature, Tmice = final ice-melting temperature
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CASANOVA ET AL.
Pyrite: Primary internal textures were preserved in
pyrite, and a few trails with fluid inclusions of various sizes
(5–150 µm), all of which appeared opaque due to internal
reflections, were obtained in both experiments pyrite-1 and
pyrite-2. All fluid inclusions analyzed by LA-ICP-MS turned
out to have been created during the autoclave experiment (see
below and Digital App 6., Table A2). For microthermometry,
a fluid inclusion from a natural sample from the San Cristobal
deposit (Peru) was used (sample FPE-004, studied in detail
by Ortelli, 2015). Visual observation can only be made with
the Hamamatsu camera and by removing the thermal-reflec-
tion filter, because this pyrite sample (Fig. 3B) has a bandgap
at around 1,351 nm, similar to those found by other authors
(Bither et al., 1968; Lüders and Ziemann, 1999; Kouzmanov
et al., 2002). The Tmice deviation curve acquired without
removing the thermal-reflection filter was recorded using a
cycling method, removing the thermal-reflection filter during
the cooling runs.
During microthermometry, the pyrite behaved similarly to
the other minerals (Fig. 9). There was no effect of light source
intensity when both diaphragms were nearly closed, and
recorded Tmice remained close to the true Tmice of –2.6°C.
Upon opening the diaphragms, the recorded Tmice shifted
toward lower values. The lowest recorded value was –33.4°C.
This result strongly contrasts with published data, which
showed a maximum shift of 0.3°C in Tmice from –4.2°C at low
light intensity to –4.5°C at the highest light intensity (Zhu et
al., 2013). However, these authors did not report the power at
which the lamp was operated nor describe their microscope
settings (diaphragm apertures, presence or absence of filters
and polarizers), thus results cannot be directly compared.
The effect of placing a thermal-reflection filter when both
diaphragms were fully open was nearly equivalent to reducing
both diaphragm apertures by 50% (Fig. 9).
Stibnite: The stibnite cylinder became very soft during the
experiment. It deformed in a ductile manner when attached
fine-grained material was scratched off with a razor blade
and the sample was bent (Fig. 5A). The area that hosts fluid
inclusions has a very low transmittance (Fig. 3B) and the
bandgap is found at 880 nm. Its absorption curve is nearly
flat close to 60% (Fig. 6). Only few and small (<8 µm) fluid
inclusions were obtained in stibnite (Fig. 5A). The aver-
Light
power (W) age Tmice was –7.2°C (n = 7) under ideal measuring condi-
tions, identical to the value obtained in the associated quartz
(Table 4). Important shifts were recorded in Tmice upon
increasing light intensity and opening diaphragms (Fig. 9),
with the lowest recorded Tmice at –46.1°C (Digital App. 4).
Although the absorption was similar to that of enargite-1
(Fig. 6), the deviation curves obtained were less pronounced
than for enargite (Fig. 9). The difference between the two
deviation curves where both diaphragms are fully open, with
and without the thermal-reflection filter, is smaller than that
observed in wolframite.
Fe-poor sphalerite: Primary internal textures of sphalerite
were preserved, although certain cracks appear more transpar-
ent than their surroundings (Fig. 5D). As a result of the very
high transmittance of Fe-poor sphalerite in the NIR region
(up to 80%; Fig. 3B), it has a very low absorption, dropping
from 20% at 800 nm to nearly 5% from 1,100 nm onward (Fig.
6). Several cracks containing numerous fluid inclusions, with
 FLUID INCLUSION STUDIES IN OPAQUE ORE MINERALS: PART II 1873

Light source power (W) Light source power (W)

0 10 20 30 40 50 0 10 20 30 40 50

-5 -5

-10 -10

-15 -15

-20 -20

-25 -25

Wolframite FI 1 Enargite 1
-30 -30
0 0

-5 -5
Tmice (°C)

Tmice (°C)
-10 -10

-15 -15

-20 -20

Pyrite Enargite 2
-25 -25
0 0

-5 -5

-10 -10

Fe-poor sphalerite 1

-15
0 1 2 3 4 5 6 7
Light source voltage (V)
Diaphragm settings
-20 Symbol Filter
Field Condenser
/ ≈0% 0.1 TRF / none
Stibnite
/ 10% 0.3 TRF / none
/ 50% 0.3 TRF / none
0 1 2 3 4 5 6 7 100% 0.65 TRF
Light source voltage (V) 100% 0.65 none

Fig. 9. Impact of light source and microscope settings on recorded final ice-melting temperature (Tmice) for fluid inclusions
(FIs) in different hosts. For each mineral only Tmice of one fluid inclusion is reported. Because the pyrite bandgap is at 1,350
nm, the fluid inclusion can only be seen by removing the thermal-reflection filter and using the Hamamatsu camera. For this
reason, for the three first diaphragm settings two symbols are proposed, one with the filter in place (TRF) and one without
(none). See text for explanation on how the deviation curve without removing the TRF was acquired. Data are only reported
for a light source operating power up to 50 W. See Digital Appendix 3 for data over the complete 100-W operating power
range of the light source.

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by Univ de Geneve UNIGE-Biblio SC Terre Enviornment, Kalin I. Kouzmanov
 1874 CASANOVA ET AL.

Fe-rich sphalerite: Experiments with Fe-rich sphalerite

A Lamp power (W)
were carried out twice with the same settings (Table 2), and
0 20 40 60 80 100 120
20 both resulted in the creation of few (less than 10) cracks con-
taining numerous fluid inclusions ranging from a few micro-
Phase-change temperature (°C)

meters up to 30 µm. However, all fluid inclusions are opaque

0 due to internal reflections, and therefore, microthermometry
could not be performed. Laser ablation-ICP-MS analyses of
single fluid inclusions (see below and Digital App. 6, Table
-20 A2) show, based on their Na content, that they were created
during the autoclave experiment.
Hematite: The chips recovered from the two experiments
-40 conducted with hematite (Table 2) were completely opaque
to NIR light. According to their optical properties and Raman
spectra, they can still be defined as hematite. In chips from
-60 both experiments, trails of holes crosscutting the chip could
be observed on the section surface in reflected light. Laser
ablation-ICP-MS analyses by blind shooting in trails of holes
B Lamp power (W)
left by opening of fluid inclusions during polishing revealed
0 20 40 60 80 100 120
that synthetic FIs were successfully created in this experiment
Deviation from true T (°C)

too (Fig. 11C).

-5
-10
-15
-20
Tmice Tmclath
Fig. 10. (A) Impact of light source power on three phase-change tempera-
tures for a fluid inclusion in enargite-2 at fixed microscope settings (ther-
mal-reflection filter on, field and condenser diaphragms at 50% and 0.3,
respectively). Phase-change temperatures are final ice-melting temperature
(Tmice), final gas-hydrate clathrate-melting temperature (Tmclath), and freez-
ing temperature (Tfreeze). (B) Comparison of the three phase-change temper-
atures as a deviation from the corresponding true temperature as a function
of the light source power.
sizes ranging from a few micrometers up to more than a hun-
dred micrometers, were obtained during the autoclave exper-
iment (Fig. 5D). However, most fluid inclusions are opaque
due to internal reflections. Microthermometry experiments
showed that phase-change temperatures were less affected
by light intensity than in the other minerals (Fig. 9). Under
ideal measuring conditions, Tmice was recorded at –7.6°C (n =
4), similar to that in the associated quartz (Table 4); the most
extreme value recorded was –14.6°C. A second experiment
with a starting solution of 5 wt % NaCl equiv yielded only
opaque fluid inclusions due to internal reflections, preventing
microthermometry measurements.
LA-ICP-MS analysis of individual fluid inclusions
Elemental contents of 355 FIs hosted in quartz and opaque
ore minerals analyzed by LA-ICP-MS are reported in Digital
Appendix 6, Tables A1 and A2, respectively. Typical LA-ICP-
MS signals obtained in quartz during FI ablations are com-
pared to those obtained in the corresponding opaque in Figure
11 for Fe-poor sphalerite-1, Fe-rich sphalerite, pyrite-1,
hematite-2, and wolframite experiments and in Figures 12B
Tfreeze and C for the enargite-2 experiment. Major elements of each
opaque mineral were found in the FIs hosted in the associated
quartz with the exception of S, which had a high background,
and Fe in the hematite experiment. Similarly, Si had a high
background and was never detected in FIs hosted in opaque
minerals. We used Cs as an internal standard; therefore, the
only elements that can be compared between FIs hosted in an
opaque mineral and those hosted in the associated quartz are
Na and, when present, Au.
Sodium content of fluid inclusions in different hosts: Aver-
age Na contents of FIs hosted in opaque minerals are com-
pared to those hosted in the quartz from the same autoclave
experiment (Fig. 13) and are reported in Digital Appendix 6,
Tables A1 and A2. For all experiments, average Na values plot
close to or below the 1:1 line, i.e., in the field where FIs in
quartz are enriched compared to those in the opaque mineral
(Fig. 13A). Sodium concentrations in FIs hosted by wolfram-
ite, the two Fe-rich sphalerite, the two Fe-poor sphalerite,
and the enargite-1 experiments plot, within error, on the
1:1 line (Fig. 13A). The hematite, enargite-2, and two pyrite
experiments show a 20 to 30% Na excess in FIs in quartz
compared to those in the opaque mineral (Fig. 13A). For all

Fig. 11. Typical laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) transient signals obtained in
fluid inclusions hosted in quartz and an associated opaque mineral. Major elements of the host mineral and Na are shown in
thicker lines. Only elements detected in fluid inclusions, Au, and major elements of the associated mineral during autoclave
experiments are reported. (A) LA-ICP-MS signals from Fe-poor sphalerite-1 experiment. The Au signal correlates with that
of Pb, and their variations are not necessarily related to the presence of fluid inclusions. (B) LA-ICP-MS signals from the
Fe-rich sphalerite experiment. (C) LA-ICP-MS signals from the hematite-2 experiment. Iron is not detected in quartz-hosted
fluid inclusions. (D) LA-ICP-MS signals from the wolframite experiment. The Au signal in wolframite-hosted fluid inclusions
is masked by the Au signal of the wolframite. (E) LA-ICP-MS signals from the pyrite-1 experiment.

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 FLUID INCLUSION STUDIES IN OPAQUE ORE MINERALS: PART II 1875

A Cps Cps Cps

108 Quartz Fe-poor Fe-poor
Pb sphalerite sphalerite
107 107
107 Cs
Zn
Si Au Na
106 106
106 Si
S S Na S
Pb
Na 105 Cs 105
105
Au Pb
104 104 104
Zn
103 103 Zn
103
Au
Cs
102 10 2
10 2

101 101 101

0 20 40 60 80 100 120 s 0 20 40 60 80 100 s 0 20 40 60 80 100 s

B Cps
108 Quartz
Cps
Fe-rich Zn
C Cps
Quartz
sphalerite
107 107
107
Si Si
106 106 Na
106
S S Fe
Au
Na 105 105
105 Pb Na
Cs
Au Cs 104
104 104
Au Cs
Pb Fe
103 103 103
Zn

102 102 102

101 101 101

0 20 40 60 80 100 s 0 20 40 60 80 s 0 20 40 60 80 100 s
D Cps
108 Quartz
Cps
Wolframite W
Cps
107 Hematite Fe

107
107 Mn Si
106
Cs Na
Si 10 6 Si
106 Au Fe
Na 105
105 Na Au
10 5

104 Cs
W
104 104
Mn
103
103 Fe 103
Au
Cs
102
102 10 2

101 101
101
0 20 40 60 80 100 s 0 20 40 60 80 s 0 20 40 60 80 s
E Cps
10 8
Quartz Si
Cps
10 8
Pyrite S

107 107 Fe
Au
Fe
106 106
S Si
Na
105 Na 105
Cs
Au
104 104

Cs
103 103

102 102

101 101
0 20 40 60 80 100 120 s 0 20 40 60 80 s

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 1876 CASANOVA ET AL.

108 Natural enargite A 108

Enargite after experiment B
Cu
107 107

Sb Cu
106 106
S Bi (470 ppm)
Na
Intensity (cps)

Intensity (cps)
S
105 105
As
Bi (302 ppm)
As
104 104 Cs
Au (208 ppm)

103 103
Au (0.5 ppm)

102 102

101 101
0 20 40 60 80 t (s) 0 20 40 60 80 t (s)

Quartz C
108

D
107

Si
106
Intensity (cps)

S
10 5 Na

As
104
Cs

103
Au
Bi-Au
nugget
102

10 µm
101
0 20 40 60 80 100 t (s)
Fig. 12. (A) Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) transient signal of a natural enargite
sample that was not used in autoclave experiments (40-µm ablation pit diameter). (B) Typical LA-ICP-MS signal obtained
on synthetic fluid inclusion hosted in enargite-2. After the autoclave experiment the Au signal is correlated with that of Bi
(ablation pit diam = 40 µm). (C) LA-ICP-MS signal from fluid inclusion hosted in quartz associated with the enargite-2
experiment. (D) Backscattered electron (BSE) image of enargite after the autoclave experiment. White dots are Bi-Au solids,
usually <<1 µm in diameter. The red circle approximates a 40-µm diameter of the laser pit used for analyses.

experiments, Na average concentrations in quartz (between
2.12 and 2.35 wt % and between 4.14 and 4.88 wt %; Table 6)
are slightly higher than the expected values (1.97 and 3.9 wt %
for 5 and 10 wt % NaCl equiv solutions, respectively), but
remain within the standard deviation except for the enargite-2
and hematite-2 experiments. In the opaque minerals, the dif-
ference between expected Na values and measured ones lie
within the analytical standard deviation except for the two
pyrite and the Fe-rich experiments (Table 6).
Gold behavior in the fluids: The gold content of individ-
ual FIs is reported in Digital Appendix 6, Tables A1 and A2.
Average Au content in FIs is highly variable between experi-
ments—from 2 ppm in quartz from the hematite experiment
to 680 ppm in quartz from the pyrite-1 experiment (Table 6).
It is also highly variable within single samples. When the Au
content is assessed in both the opaque mineral and the associ-
ated quartz, concentrations are similar within one standard
deviation, with the exception of the two Fe-poor sphalerite

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 FLUID INCLUSION STUDIES IN OPAQUE ORE MINERALS: PART II 1877

A B
6 1000 1:1
30% 1:1 2:1
20% Sl-2 2:1

Py-1

FI in opaque Au (ppm)
5 20% Py-2
FI in opaque Na (wt%)
Sl-1

30%
100
4

3
10

1 2 3 4 5 6 1 10 100 1000
FI in quartz Na (wt%) FI in quartz Au (ppm)
Wolframite Enargite Hematite Pyrite Fe-rich Sphalerite Fe-poor Sphalerite

Fig. 13. (A) Average Na content of synthetic fluid inclusions (FIs) hosted in opaque minerals compared to the fluid inclu-
sions hosted in the associated quartz. Dashed 20 and 30% lines mark a 20 and a 30% deviation from the 1:1 line, respectively.
(B) Average Au content in fluid inclusions hosted in pyrite, Fe-rich sphalerite, Fe-poor sphalerite, and the fluid inclusions
hosted in the associated quartz. Important Au content in Fe-poor sphalerite-hosted fluid inclusions compared to quartz may
be explained by Au incorporation into the sphalerite (see text). Gold content in hematite-, enargite-, and wolframite-hosted
fluid inclusions could not be assessed. Error bars correspond to the standard deviations.

experiments where Au contents in FIs in Fe-poor sphalerite
are an order of magnitude higher than those hosted in quartz
(Fig. 13B; Table 6). The LA-ICP-MS Au transient signal in
Fe-poor sphalerite correlates with that of Pb, and the varia-
tions are not necessarily related to the presence of FIs (Fig.
11A). Rather, Au appears as a trace element with variable con-
centration within the crystal, and consequently it is difficult to
define a portion of the host signal representative of the host
surrounding the inclusion. If this portion has lower Au and Pb
content than the FIs surrounding, Au and Pb concentrations
in the fluid will be overestimated even with a host correction
of the signal. As a result of the host correction process, Au con-
tents of Fe-poor sphalerite-hosted FIs have to be treated with
caution and may not represent the Au content of the trapped
fluid. Gold content could not be assessed in the wolframite
and the enargite experiments, as the LA-ICP-MS signal has
the appearance of a trace element in the host minerals (Figs.
11D, 12B, respectively). In these examples, the Au LA-ICP-
MS signal from the FIs is masked by the signal from the
host. The Au signal in enargite that underwent the autoclave
experiment correlates strongly with the Bi signal (Fig. 12B),
but this is not the case in samples that did not undergo auto-
clave experiments (Fig. 12A). High-resolution scanning elec-
tron microscopy-backscattered electron (SEM-BSE) imaging
reveals numerous 1-nm to 0.87-µm blebs of Bi-Au–bearing
solid inclusions in enargite after the heating experiment (Fig.
12D). In contrast, the correlation of Au with W (Fig. 11D)
in wolframite is most likely due to polyatomic interferences
(183W14N or 185W12C). In this case, the measured Au content
in FIs hosted in the associated quartz could be overestimated.

Table 6. Sodium and Gold Average Concentrations, Medians, and Standard Deviations of Fluid Inclusions
Hosted in the Opaque Mineral and its Associated Quartz

       Quartz       Opaque

NaCl Median Average Median Average Median Average Median Average

Experiment (wt %) Na (ppm) Na (ppm) σ (Na) Au (ppm) Au (ppm) σ (Au) Na (ppm) Na (ppm) σ (Na) Au (ppm) Au (ppm) σ (Au)

Enargite-2   5 24,641 23,523 2,817 174 217 130 19,496 19,564 1,961 n.q. n.q.
Enargite-1 10 41,908 41,357 4,736 467 626 465 36,142 39,058 9,028 n.q. n.q.
Hematite 10 47,917 48,858 3,554    0 2 8.5 44,088 42,337 8,422 <LOD <LOD
Pyrite-1 10 43,382 43,343 6,418 631 679 380 34,511 35,037 2,956 341 415 307
Pyrite-2   5 21,439 21,302 2,386 370 353 110 16,805 16,985 1,798 316 335   91
Wolframite 10 45,676 44,401 6,472   49 51   17 44,643 42,864 4,372 n.q. n.q.
Fe-poor Sl-1 10 43,321 44,079 4,720   68 72   33 40,620 41,768 3,450 204 209 187
Fe-poor Sl-2  5 20,566 21,240 2,969  52 56  27 21,724 21,957 1,285 484 551 294
Fe-rich Sl  5 23,426 23,375 1,241  28 28   9 21,925 22,720 2,401  13  23  22
Stibnite 10 44,605 44,337 5,468  39 40  23 n.a. n.a. n.a. n.a.

Abbreviations: <LOD = below limit of detection, n.a. = not analyzed, n.q. = not quantifiable due to high Au signal in the host, Sl = sphalerite

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by Univ de Geneve UNIGE-Biblio SC Terre Enviornment, Kalin I. Kouzmanov
 1878
Discussion
NIR light fluid inclusion microthermometry in opaque ore
minerals: possibilities and limitations
When comparing the Tmice deviation curves (Fig. 9) of a
low-absorption mineral, such as the Fe-poor sphalerite, with
high-absorption minerals (e.g., pyrite, stibnite, wolframite,
enargite; Fig. 6), it appears that absorption is a controlling
factor of the extent of the registered deviations. The absorp-
tion of a mineral, which was defined above as the amount of
light (in %) that is neither reflected nor transmitted, therefore
depends in part on the sample transmittance.
Transmittance obeys the Lambert-Beer law, which links
it to the thickness of the sample and the absorption coeffi-
cient. Applying the Lambert-Beer equation (eq. 3) to the light
effectively entering the sample, i.e., subtracting reflected light
to the incident light, it is possible, for any wavelength (λ), to
calculate the absorption coefficient of a sample of known
transmittance (Tref) at a known thickness (dref) and known
reflectance (R). The reflectance only depends on the wave-
length and intrinsic parameters, such as the extinction coef-
ficient and the refractive index and, therefore, is assumed
independent of thickness. Using equation (3), the transmit-
tance can be expressed as a function of the thickness (d) and
the above-mentioned known parameters (see Digital App. 7
for a detailed calculation):
         I (
                            d      Tref(dref, λ)
                            —–⋅ln ————–
t(d, λ)             dref      1 – R(λ)
T(d, λ) = ——— = (1 – R(λ))⋅e                   . (7)
( ))
           I0
The effect of thickness variation on transmittance has been
simulated using equation (7) and is presented in Figure 14. As
illustrated in Figure 14, decreasing the thickness of a sample
not only augments the transmittance at any given wavelength
but also widens transmittance bands. The maximum trans-
mittance is limited by the reflectance as illustrated in Figure
T (%)
100
Hamamatsu C2400-03d
Olympus XM10
80
60
40
20
0 0
800 1000 1500 2000 2500
Fig. 14. Simulation of the effect of thickness variation on transmittance of (A) enargite-2 and (B) wolframite zone 1. Simu-
lation applies the Lambert-Beer law to the reference spectra acquired on 150-µm-thick samples, assuming reflectance is
independent of the thickness, to provide theoretical transmittance curves. The Fabry-Perot interferences (high-frequency
oscillations on spectra) were not corrected for the effect of thickness on their frequency (frequency should decrease with
thickness).
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CASANOVA ET AL.
14A, between 2,200 and 2,700 nm, where there is therefore
no absorption.
The absorption coefficient is proportional to the extinction
coefficient. Some anisotropic minerals may have very differ-
ent extinction coefficients along each principal index of refrac-
tion. For instance, in stibnite, values of 0.651 and 1.436 for
the extinction coefficient at 589 nm were found perpendicu-
lar to the (100) and (001) crystallographic planes, respectively
(Schubert and Dollase, 2002). Consequently, twinned minerals
may exhibit strongly variable absorption in different crystal-
lographic orientations. The extent of the influence of mineral
orientation on the deviation curves was not investigated here.
For a given mineral the NIR transmittance can be highly
variable, as demonstrated by Lüders (2017). Detailed com-
bined FTIR, electron microprobe analysis (EMPA), and
LA-ICP-MS study of IR transmittance and trace element
distributions in zoned opaque ore minerals by Ortelli et al.
(2018) has revealed that variations in trace element composi-
tion have a strong influence on the transmittance of a mineral.
The extinction coefficient varies with composition (Muller et
al., 2009), and within the same mineral grain the composi-
tional variations between growth zones may result in strongly
variable absorption. As shown in Figure 8B, zones with con-
trasting absorption spectra will require different light intensi-
ties when performing microthermometry. Consequently, sets
of deviation curves (i.e., obtained at different light power and
microscope settings) will be different for each part of the sam-
ple with a different composition.
When comparing the deviation curves obtained in enar-
gite-2 and in pyrite, it appears that although enargite-2 has
a much lower absorption it is affected by stronger Tmice
deviation. Stibnite and enargite-1 have similar absorption
curves (Fig. 6), and yet the Tmice deviations recorded in stib-
nite are smaller (Fig. 9). These two examples indicate that
absorption is not the only factor controlling the Tmice devia-
tions and that the ability to dissipate accumulated heat also
T (%)
A 100
B
Hamamatsu C2400-03d
Olympus XM10
80
50 µm
80 µm
60
100 µm
150 µm
40 50 µm
200 µm
250 µm
80 µm
300 µm
100 µm
20
150 µm
200 µm
250 µm
300 µm
3000 λ (nm) 800 1000 1500 2000 2500 3000 λ (nm)
 FLUID INCLUSION STUDIES IN OPAQUE ORE MINERALS: PART II 1879

plays an important role. In a solid, heat can be dissipated by the tungsten-halogen light source used is emitted. If the slope
radiation or conduction. In the range of temperature of con- difference was due to variation of the thermal conductivity
cern in microthermometry, where temperature usually does coefficient with temperature (Clauser and Huenges, 1995)
not exceed 600°C, radiative transfers governed by the Ste- the shift curve (Fig. 10B) corresponding to the Tmclath, the
fan-Boltzmann law (eq. 2) can be neglected. Therefore, the highest of the three temperatures, would not lie between
temperature of the sample depends only on the competition those of Tmice and Tfreeze.
between radiative heating from the light source and energy To summarize, the shift between the recorded phase-
dissipation via conduction that will result in a temperature change temperature and the true temperature depends on
gradient between the part of the sample affected by the light how much light effectively reaches the sample, the absorption
beam and the parts that are not. This gradient depends on the of the mineral, and its thermal conductivity and results from
thermal conductivity of the sample (eq. 5). Data on thermal a competition between radiative heating from the light source
conduction of opaque minerals are scarce in the literature. and conductive cooling. In contrast to the results reported by
Published data show that pyrite has a thermal conductivity Moritz (2006), for all tested minerals the obtained deviation
about an order of magnitude higher than enargite and vari- curves tend follow a third-order polynomial trend (Fig. 9)
ations of up to 20% between different pyrite samples from rather than a linear one, independent of whether the curves
different localities (Table 7). Because of its higher thermal are plotted against the light intensity or against the light power.
conductivity, pyrite dissipates accumulated heat more readily Since the deviation curve depends on mineral composi-
than enargite, thereby explaining why pyrite has smaller Tmice tion, the phase-change temperature, the microscope settings,
deviation curves than enargite-2 (Fig. 9) despite their similar and the light source and its power, creating calibration curves
absorption spectra (Fig. 6). Even though there are no ther- becomes impracticable, as deviation curves obtained on one
mal conductivity data available for stibnite, a similar process is FI for a given phase-change temperature cannot be applied to
invoked to explain the smaller deviations recorded in stibnite another phase-change temperature (Fig. 10) or another loca-
compared to enargite-1 (Fig. 9). tion (Fig. 8). It is therefore not possible to create standards for
Deviation curves obtained on FIs close to the upper surface NIR microthermometry.
are indistinguishable from the ones close to the lower surface. Measurements acquired in this study used to establish the
According to the Lambert-Beer law, the amount of light trans- deviation curves were performed using a Linkam stage. How-
mitted and therefore available to be absorbed decreases expo- ever, the first study that demonstrated the important effect
nentially with thickness. It can be concluded that the slab is of light source intensity on recorded phase-change tem-
too thin to allow a measurable vertical temperature gradient. peratures was based on microthermometric data acquired
Repeated results obtained on three phase-change tem- with a USGS gas-flow stage (Moritz, 2006). When perform-
peratures from one FI in enargite-2 (Fig. 10A) exhibit three ing microthermometry with such a stage, the shift between
deviation curves with significantly different slopes. The com- true and recorded phase-change temperature will still result
position of the fluid, the presence of solids, and the fluid/solid from competition between radiative heating from the light
ratio constantly change during microthermometry, and as a source and conductive cooling. However, the design of the
result the transmittance and therefore the absorption of the gas-flow stage, in which the sample is cooled by a flux of cool
FI is expected to vary. Yet the fact that these three deviation air, will enhance cooling of the sample through forced convec-
curves show different slopes is surprising, because radia- tion at the surface of the sample. Therefore, deviation curves
tive energy from the light source is mainly absorbed by the obtained using a USGS stage are expected to have slightly
enclosing mineral, which remains constant, and not by the FI different shapes than those obtained using the Linkam stage.
itself that suffers the phase changes. Indeed, most gases, gas- Nevertheless, shifts up to several hundred percent between
hydrates, water, and ice are absorbent in the mid- and far- true and recorded temperatures can still occur (Moritz, 2006).
infrared regions (Richardson et al., 1985; Lynch, 2005) rather
than in the near-infrared region where most of the energy of Comparing fluids trapped in opaque minerals and quartz
Density distribution and size are not comparable between
cosynthesized FIs in quartz and opaque minerals. Many
Table 7. Compilation of Thermal Conductivities for fewer fractures are created in opaque minerals than in quartz.
Different Minerals from the Literature
Final Tmice recorded under ideal measuring conditions in the
Thermal opaque mineral are similar to those recorded in the associated
conductivity Temperature quartz within analytical uncertainty (Table 4). This shows that,
Mineral (W.m-1.K-1) (K)/°C Source if using ideal measuring conditions, samples containing the
same fluid show the same microthermometric behavior, irre-
Pyrite 25.4 308/35 Diment and Pratt (1988)
Pyrite 20.5 308/35 Diment and Pratt (1988) spective of whether the host is transparent or opaque.
Pyrite 19.2 N/A Horai and Simmons (1969) Expected Tmice for the two prepared starting solutions of 5
Sphalerite 11.3 308/35 Diment and Pratt (1988) and 10 wt % NaCl equiv are –3° and –6.6°C, respectively. With
Sphalerite 12.5 308/35 Diment and Pratt (1988) the exception of the enargite-2 and hematite-2 experiments (5
Sphalerite 12.7 N/A Horai and Simmons (1969)
Enargite   3.2 300/27 Böhm et al. (1985)
and 10 wt % NaCl equiv, respectively) all ice-melting points
Hematite 12.42 ± 1.74 303/30 Clauser and Huenges (1995) (independent of whether measured in opaque minerals or in
Hematite 11.3 N/A Horai and Simmons (1969) quartz) are slightly lower than the values expected from the
starting solution (Table 4). The chosen natural opaque sam-
N/A = not applicable ples contained only few natural FIs and, given the amount of

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by Univ de Geneve UNIGE-Biblio SC Terre Enviornment, Kalin I. Kouzmanov
 1880
starting solution (nearly 10 wt % of the opaque), mixing with
highly saline fluids trapped in natural FIs cannot account for
the observed lowering of the Tmice. Rather, the LA-ICP-MS
data, the presence of daughter minerals, and the presence of
gas-hydrate in the enargite experiments suggest that partial dis-
solution of the opaque minerals occurred during equilibration
prior to quenching. This resulted in a trapped fluid that has
additional components compared to the starting composition.
The higher entropy of the equilibrated solution relative to the
starting composition leads to a water activity decrease, which
therefore increases the freezing-point depression (Steele-
MacInnis et al., 2016; Wilkinson, 2017). This is the case in most
experiments, where recorded Tmice is lower than the expected
Tmice. A notable discrepancy is found in the hematite-2 experi-
ment, where the recorded Tmice of –6°C in the associated
quartz implies a salinity decrease of the solution. At the experi-
mental conditions (Table 2), this cannot be explained by NaCl
saturation within the capsule. As mentioned above, dilution by
fluids present in natural FIs is unlikely. Alternatively, it may be
due to leakage and dilution by the water that acted as a pressure
medium, as the significant change in the capsule weight during
experiment may suggest (Table 2).
The good reproducibility of Tmice recorded over a popu-
lation of FIs in each experiment suggests that equilibrium
between the fluid and minerals was reached prior to fluid
entrapment. This is further supported by the similar Na/Cs
ratios determined by LA-ICP-MS in FIs hosted in opaque
minerals and FIs hosted in quartz from the same experi-
ment. Gold concentrations are generally less reproducible,
which can be partly explained by Au incorporation into the
opaque mineral phase itself (e.g., sphalerite, but also enar-
gite; see Fig. 12). In sphalerite-hosted FIs, the Au content is
an order of magnitude higher than in associated quartz (Fig.
13). In sphalerite, Au correlates with Pb where they appear as
trace elements with varying concentrations. Fluid inclusions
seem to be concentrated in Au-Pb–richer zones (Fig. 11A) for
which it can be challenging to define a portion of the LA-ICP-
MS signal representative of the host immediately surrounding
the FIs. Therefore, even when applying a host correction to
the signal, calculated Au values in FIs may be overestimated
if the defined host portion has lower Au and Pb than the one
immediately surrounding the FIs.
A significant amount of gold (up to 680 ppm) can be dis-
solved from the capsule. Gold content in the synthetic FIs
is highly variable from one experiment to another, and com-
prehension of the mechanisms behind gold transport in the
fluid and scavenging of Au by elements present in the mineral
structure is beyond the scope of this study.
Recommendations
The present work shows that microthermometry determina-
tions are always affected by the light source intensity when
the thermal-reflection filter is removed. In certain cases, as in
enargite, the shift between the true phase-change temperature
and the observed is up to several tens of degrees. The magni-
tude of the shift depends mostly on mineral composition, over
which one has little control. However, we show (Fig. 9) that for
any NIR-transparent mineral there is a range of light source
power and microscope settings where the shift is acceptable
for microthermometric studies on crustal fluids, and those have
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by Univ de Geneve UNIGE-Biblio SC Terre Enviornment, Kalin I. Kouzmanov
CASANOVA ET AL.
been defined above as ideal measuring conditions. Therefore,
before performing any microthermometry experiments it is
necessary to define those ideal measuring conditions. For this
purpose, deviation curves must be acquired to target the range
of light and microscope settings under which the results are not
significantly affected by local heating effects.
In addition to the obvious need to limit the sample thick-
ness, which will increase exponentially the opacity (Fig. 14)
and thus increase the light power that is needed for observa-
tion, with correspondingly stronger absorption effects in the
sample, the following recommendations may help to refine
these ideal measuring conditions:
1. Using a 50-W lamp is enough, as most minerals show sig-
nificant shifts when the lamp is operated at higher power.
2. The use of filters is strongly recommended—at least to cut
wavelengths that are longer than the camera cutoff. Ideally,
systematic acquisition of FTIR absorption spectra will help
in selecting the appropriate combination of low- and high-
pass filters to target the less absorbing part of the spectra.
3. When working with anisotropic minerals, especially
strongly bireflectant ones, using a polarizer will help to
remove the influence of the most absorbing refractive
index.
4. The polarizer can also be used to restrict the influence of
shorter wavelengths when no high-pass filters are available.
These recommendations are summarized in Figure 15.
It is important to repeat this work even in a single crystal if
there are strong variations in transmittance between different
Sample preparation
(thickness: ~ 200 to 100 µm) Adjust thickness
optimize transmittance
NIR petrography
FTIR Absorbance
from reflectance & transmittance spectra
Low-pass filter
(camera upper limit)
Band-pass filter
target less-absorbing part of spectra
Define ideal measuring conditions
Acquire Tmice deviation curves as a function of light source
power and microscope settings
Microthermometry data acquisition & reporting
phase change temperature, light source power, microscope
settings (diaphragm aperture), type of filters
Fig. 15. Flow sheet illustrating considerations to be assessed prior to near-
infrared microthermometry of a fluid inclusion assemblage hosted by an
opaque mineral. See “Recommendations” section for details. Abbreviations:
FTIR = Fourier transform infrared, NIR = near-infrared, Tmice = final ice-
melting temperature.
 FLUID INCLUSION STUDIES IN OPAQUE ORE MINERALS: PART II
zones. Not doing so may result in important underestima-
tion of phase-change temperature that will in turn result in
important overestimation of salinity. Therefore, any NIR
microthermometry study should report the way in which the
ideal measuring conditions have been reached. Failing to do
so would cast serious doubts on the results obtained.
Conclusions
For the first time, FIs were successfully cosynthesized in
quartz and a range of opaque minerals commonly found in
various hydrothermal ore deposits. To achieve equilibration of
the fluid with the minerals, an autoclave with in situ quench-
ing capacities was used. This was necessary, as some minerals
are more readily soluble than quartz and may release, upon
dissolution, cations that will affect microthermometry. We
have also demonstrated that some minerals present in the
experiment, particularly sulfides, help to solubilize Au from
the capsule, leading to concentrations in the fluid of up to
680 ppm. This Au has also been incorporated in some of the
opaque minerals, either as nano- to submicrometric inclu-
sions (Bi-Au nuggets in enargite) or as a trace element, which
can hamper, if not render useless, LA-ICP-MS analyses of the
Au content of FIs.
It has been shown that cosynthetic FIs in quartz and opaque
minerals trap the same fluid within the precision of microther-
mometry and LA-ICP-MS analysis. Absorption processes are
inherent to opaque minerals and depend on intrinsic parame-
ters that may significantly vary within a sample. It is therefore
not possible to create standards for NIR microthermometry.
Absorption causes local overheating of the sample; as a
result, the temperature recorded by the thermocouple is
lower than the actual temperature of the phase transition.
The observed shift between true and recorded temperature
(up to several tens of degrees) depends on the intensity of the
incoming light and on the capacity of the sample to lose heat
through diffusion. The gradient established within the sample
that results from the competition between absorption and
dissipation processes is temperature dependent. As a result,
deviation curves acquired on one FI over a chosen phase-
change temperature cannot be used as calibration curves for
other FIs or phase-change temperatures.
We have, however, demonstrated that for every mineral
it is possible to define a range of settings (ideal measuring
conditions) where recorded phase-change temperatures are
not biased. These settings can be controlled by the user and
include light source power, both diaphragm apertures, and
the use of filters. Because these ideal measuring conditions
vary not only between samples but also within a given min-
eral, it is critical to define them prior to any NIR microther-
mometry work by acquiring deviation curves for a chosen FI
at different settings.
Following the recommendations discussed above, and
using ideal measuring conditions, reliable and reproducible
data can be obtained using NIR microthermometry, and
thus knowledge of pressure-volume-temperature-composi-
tion (PVTX) properties of fluids can be gained from certain
opaque minerals in a manner similar to that from transparent
minerals. Not following these recommendations may result
in important underestimation of phase-change temperatures
that will, in turn, result in important overestimation of salinity.
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by Univ de Geneve UNIGE-Biblio SC Terre Enviornment, Kalin I. Kouzmanov
1881
Acknowledgments
This work was supported by the Swiss National Science
Foundation (grants 200020_160071, 200021_127123, and
206021_133781) and the Bayerisches Geoinstitut (University
of Bayreuth, Germany), which provided a traveling grant for
Vincent Casanova and financial support to carry out part of
the laboratory work. We acknowledge Jean-Marie Boccard for
the thin section preparation and Agathe Martignier for her
help during SEM sessions.
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by Univ de Geneve UNIGE-Biblio SC Terre Enviornment, Kalin I. Kouzmanov
1883
Vincent Casanova obtained an engineering
diploma in economic geology and mineral explora-
tion from the Ecole Nationale Supérieure de Géol-
ogie (Nancy, France) in 2010 and an M.Sc. degree
in mineral exploration and environmental geosci-
ences from Luleå Tekniska Universitet (Sweden).
After working three years as an exploration geolo-
gist in Kazakhstan, Sweden, and Chile, he started Ph.D. studies at the Uni-
versity of Geneva (Switzerland), focused on geochemical processes leading
to the formation of a major epithermal polymetallic deposit in central Peru;
he defended his thesis in 2018. His research interests include near-infrared
microthermometry of ore minerals.
Downloaded from https://pubs.geoscienceworld.org/segweb/economicgeology/article-pdf/113/8/1861/4638232/1861-1883.pdf
by Univ de Geneve UNIGE-Biblio SC Terre Enviornment, Kalin I. Kouzmanov