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Solid Earth Sciences 3 (2018) 8e15
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Trace element analyses of fluid inclusions using laser ablation ICP-MS

Cong-ying Li a,b,*, Yu-hang Jiang c, Yan Zhao c, Chan-chan Zhang c, Ming-xing Ling d,f,
Xing Ding d,f, Hong Zhang e, Jie Li a,b,g,**
a
Center of Deep Sea Research, Institute of Oceanology, Chinese Academy of Sciences, Qingdao, 266071, China
b
Laboratory for Marine Mineral Resources, Qingdao National Laboratory for Marine Science and Technology, Qingdao, 266237, China
c
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, 511 Kehua Street, Wushan,
Guangzhou, 510640, China
d
State Key Laboratory of Isotope Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, 511 Kehua Street, Wushan, Guangzhou,
510640, China
e
Department of Geology, Northwest University, Xi'an, 710069 China
f
Center for Excellence in Tibetan Plateau Earth Sciences, The Chinese Academy of Sciences, Beijing, 100101, China
g
College of Resources, Hebei GEO University, Shijiazhuang, 050031, China
Received 5 September 2017; revised 12 December 2017; accepted 13 December 2017
Available online 10 January 2018

Abstract

Fluid inclusions are records of the physico-chemical conditions of fluiderock interactions during magmatism, mineralization and fluid
percolation and mixing processes. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a powerful tool for in situ
analyses of small samples at micrometer levels. Here we report in situ analyses of fluid inclusions using LA-ICP-MS method. NIST SRM glasses
and 23Na are generally used as external and internal standards for LA-ICP-MS analysis of fluid inclusion, respectively, although the RSD of
microthermometric estimation of 23Na is about 20% and even worse, the background signal of Na is high for most ICP-MS. Using well-
characterized natural fluids inclusion, we show that RESOlution S-155 laser system analyze fluid inclusions in quartz and determine the
trace element concentrations. Resonetics RESOlution S-155 laser has the advantage of the motorized Z stage can be used to accommodate
variation of sample height or sample topography and height difference between samples, which is very important for analyzing the fluid in-
clusion in quartz. Our results suggest laser energy density is 25 J/cm2, laser pulse repetition rates are commonly between 6 and 10 Hz to avoid
the fissuring of quartz and obtain adequate results. For this LA-ICP-MS analysis, uncertainty on 35Cl content is around 40% because of intensity
of the 35Cl signal is three orders of magnitude less intense than the intensity of the 23Na signal. Nevertheless, it is still a useful reference for fluid
inclusion analyses in addition to 23Na. This technique can be applied to a range of hydrothermal geology problems, including determining the
origins of ore forming brines and ore deposition processes, mapping metamorphic and hydrothermal fluid provinces and pathways, and con-
straining the effects of fluiderock reactions and fluid mixing.
Copyright © 2018, Guangzhou Institute of Geochemistry. Production and hosting by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: RESOlution S-155; Laser ablation ICP-MS; Fluid inclusions; Hydrothermal ore deposit; In situ analyses

* Corresponding author. Center of Deep Sea Research, Institute of 1. Introduction

Oceanology, Chinese Academy of Sciences, Qingdao, 266071, China.
** Corresponding author. School of Resources, Hebei GEO University, Shi- In the Earth, fluid plays a fundamental role in mass and heat
jiazhuang, 050031, China.
E-mail addresses: licongying18@163.com, licongying@qdio.ac.cn
transportations, encompassing all phases such as aqueous or
(C.-y. Li), lijiesue@163.com (J. Li). carbonic solutions, silicate, sulfide or carbonate melts and
Peer review under responsibility of Guangzhou Institute of Geochemistry. supercritical liquids. Minerals may incorporate tiny droplets of

https://doi.org/10.1016/j.sesci.2017.12.001
2451-912X/Copyright © 2018, Guangzhou Institute of Geochemistry. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 C.-y. Li et al. / Solid Earth Sciences 3 (2018) 8e15
fluids during crystallization. Thus, the composition of fluid
inclusions may provide key constraints on past processes of
fluid-mediated chemical transfer in Earth systems. Fluid in-
clusions in minerals are the main source of information on ore-
forming fluid evolution, hydrothermal transportation and
mineralization processes in hydrothermal ore deposits. Recent
two decades, LA-ICP-MS method with rapidly advancing has
become essential analytical tool of analyzing individual fluid
inclusions due to its excellent detection limits and fast data
acquisition capabilities (e.g (Allan et al., 2005, 2011; Audetat
et al., 1998, 2000a, b; Audetat and Pettke, 2003; Gunther
et al., 1998; Heinrich et al., 1999; Pique et al., 2008;
Richard et al., 2010; Seo et al., 2009; Ulrich et al., 1999,
2002; Ulrich and Mavrogenes, 2008; Wilkinson et al., 2009)).
NIST SRM glasses and Na are generally used as external
and internal standards for LA-ICP-MS analysis of fluid in-
clusion, respectively (Audetat et al., 1998, 2008; Gunther
et al., 1998; Ulrich et al., 1999, 2002). This usually in-
troduces large errors. First of all, the calculation of major and
trace element concentrations in fluid inclusions is usually
based on empirical equations. The RSD of microthermometric
estimation of 23Na is typically >20%. Second, the salt in fluid
inclusions are not pure NaCl as assumed. There are also KCl
and CaCl2. Moreover, the background signal of 23Na is very
high for most ICP-MS (104e106 CPS). Some researchers tried
to use Cl as the internal standard (Stoffell et al., 2004, 2008;
Wilkinson et al., 2009). Analysis of halogens by LA-ICP-
MS, however, is not a standard practice, because halogens
tend to have relatively low ionisation efficiencies that lead to
lower sensitivity, and thus higher detection limits.
In this study, we assess the method of determining in situ
trace element of individual fluid inclusions by RESOlution S-
155 laser ablation system coupled with Agilent 7900x ICP-
MS. Both 23Na and 35Cl are used to calculate the trace
element concentrations of fluid inclusions.
2. Sample preparation and analytical methods
2.1. Sample preparation
Fluid inclusions in quartz samples come from the Hujiayu
copper deposit, which is located in the Zhongtiaoshan region
on the southern margin of the North China Craton (Jiang et al.,
2014; Sun et al., 2016). The Hujiayu copper deposit is
geologically similar to the nearby Bizigou, Laobaotan, and
Tongmugou deposits and is classified as a “HueBi type”
copper deposit in literature (Jiang et al., 2014; Sun and Hu,
1993). The orebodies are hosted within dolomitic marble
and carbonaceous shales of the mid-Paleoproterozoic Zhong-
tiao Group (Sun and Hu, 1993). Red beds composed of weakly
metamorphosed hematitic siltstone and dolomitic marble un-
derlie the stratiform orebodies (Jiang et al., 2014; Wei et al.,
1984).
Five types of fluid inclusions are recognized in the Hujiayu
Cu deposit and they are: (1) pure vapor and vapor-rich in-
clusion, (2) pure CO2 inclusion, (3) CO2eH2O inclusion, (4)
liquid-rich inclusion, and (5) daughter mineral-bearing
9
inclusion (Jiang et al., 2014). Microthermometric analysis
shows that the ore-forming fluids of the early mineralization
stage are characterized by high salinity (22e40 wt. % NaCl
equiv.) and moderate temperature (120e280
C). Composi-
tions of the ore-forming fluids in the early and late stages are
interpreted to be mainly basinal brine and metamorphic hy-
drothermal solution, respectively. Carbon and oxygen isotope
compositions suggest possible carbon isotope exchange be-
tween the ore-forming fluids and organic-rich carbonaceous
shale during the early stage. In the late mineralization stage,
both degassing of CO2 and isotopic exchange with organic
carbon may have contributed to the formation of the more
negative values of mineralized carbonates. The ore-forming
fluids of the late mineralization stage are characterized by
CO2 enrichment, high salinities, high temperatures and un-
derwent significant unmixing at a temperature interval of
240e480
C (Jiang et al., 2014).
Our samples were collected from the No. 3 orebody and
were examined by both transmit-ted and reflected light mi-
croscopes and described in detail. The fluid inclusions consist
of two (liquid H2O þ CO2-rich supercritical fluid) or three
phases (vapor CO2 þ liquid CO2 þ liquid H2O) at room
temperatures. They commonly occur in lines or clusters,
mainly as negative crystals and are elliptical in shape. These
fluid inclusions are commonly ~20 mm in diameter and the
carbonic phases occupy 35e80 vol. % (Jiang et al., 2014)
(Fig. 1).
The analyzed samples all belong to L-type (liquid-rich)
inclusions, which consist of liquid and <35% vapor and S-type
(daughter mineral-bearing) inclusions, which mostly occur in
negative crystal and elliptical shapes with vapor phases
occupying 10e30 vol.% (Fig. 1). These are all formed at the
early mineralization stage. To ensure that the fluid inclusions
were representative of ore formation, only fluid inclusions
hosted within quartz and dolomite paragenetic with metal
sulfides were chosen.
2.2. Analytical methods
Microthermometry study was carried out on a Linkam
MDS 600 HeatingeFreezing System at the Key Laboratory of
Mineralogy and Metallogeny, Chinese Academy of Sciences.
Thermocouples were calibrated in the range of 196
C to
600
C using synthetic fluid inclusions. The precision of
temperature measurement is ±0.1
C between 100
C and
25
C; ±1
C between 25 and 400
C; and ±2
C for tem-
perature above 400
C. The heating rate was generally
0.2e5
C/min during the process of fluid inclusion testing, but
reduced at a rate of 0.1
C/min near the freezing point, and
0.2e0.5
C/min near the homogenization temperature to re-
cord the phase trans-formation process accurately (Jiang et al.,
2014).
The individual fluid inclusion analysis was carried out
using a LA-ICP-MS system in the CAS Key Laboratory of
Mineralogy and Metallogeny, Guangzhou Institute of
Geochemistry, the Chinese Academy of Sciences. The system
consists of an Agilent 7900x ICP-MS coupled with a
10 C.-y. Li et al. / Solid Earth Sciences 3 (2018) 8e15
Fig. 1. Microphotographs of the fluid inclusions in the Hujiayu Cu deposit.
Resonetics RESOlution S-155 laser. This laser ablation system
has the advantage of a large sample cell (155 mm  105 mm),
which can host 20 epoxy sample mounts (with diameter of
25.4 mm). Additional, the laser projection lens and the camera
system are mounted on a vertical Z motorized stage, which
provides ±5 mm of vertical travel. The motorized Z stage can
be used to accommodate variation of sample height or sample
topography and height difference between samples, which is
very important for analyzing the fluid inclusion in quartz.
Oblique viewing system is high resolution 1/3 inch color CCD
camera which is with motorized zoom and focus capability.
Two-volume laser-ablation cell can wash out 99% signal
within less than 1.5 s. A Squid smoothing device was used to
reduce statistic error induced by laser-ablation pulses and
improve the quality of data (Li et al., 2012; Tu et al., 2011).
Helium gas carrying the ablated sample aerosol is mixed with
argon carrier gas and nitrogen as additional diatomic gas to
enhance sensitivity, and finally flows into ICP. Prior to anal-
ysis, the LA-ICP-MS system was optimized using NIST610
ablated with 29 mm spot size and 5 mm/s scan speed to achieve
maximum signal intensity and low oxide rates. The spot size is
adjustable (4e200 mm) and laser pulse frequency of 1e20 Hz.
For controlled ablation of quartz-hosted fluid inclusions an
energy density above 20 J/cm2 was used and the laser pulse
frequency was set to 6 Hz.
The concentration of Na in fluids, derived from the
microthermometrically determined NaCl equivalent salinity,
was used as an internal standard to convert element ratios into
absolute concentrations. Based on initial test measurements
with a rather large suite of elements, the final multi-element
analytical package contained Si, Na, K, Rb, Cs, Ca, Mg, Sr,
Ba, Cu, Pb, Fe, Zn, Al, Fe, Mn, and Cl. Element concentra-
tions were quantified using the ICPMSDataCal software
package that allows for deconvolution of host and inclusion
signals (Lin et al., 2016). For most elements, NIST 610 was
used as external reference material (Guillong et al., 2008;
Gunther et al., 1998). All fluid inclusion signals were care-
fully screened, and for each element only signals with clearly
visible peaks above 3s (background) that followed the large
Na and Cl peak were used for calculation of element con-
centrations. The detailed instrumentation and operating con-
ditions are given in Table 1. The presence of accidentally
trapped mineral in very few fluid inclusions was always
detected in the time-resolved ICP-MS signals and these data
were not further considered.
3. Results
3.1. Microthermometric results
The results of the microthermometric analyses of the fluid
inclusions are summarized in Table 2. For L-type inclusions,
the first melting temperatures focus on 68
C (Table 2),
which suggest that the fluids are H2OeNaCleCaCl2 systems
to estimate salinity (Chi and Ni, 2007; Oakes et al., 1990). Ice
melting temperatures of the L-type inclusions is 31.7
C,
 C.-y. Li et al. / Solid Earth Sciences 3 (2018) 8e15 11

Table 1 inclusions range from 190
C to 243
C, with corresponding

LA-ICP-MS instrumentation and operating conditions. salinities of 32.1e35.1 wt. % NaCl equiv.
Resolution S-155 laser ablation system (ArF Excimer, Resonetics LLC,
USA) 3.2. Chemical composition of the fluid inclusions
Laser wavelength 193 nm
Pulse width ~20 ns
Fluence 25 J cm2 In the first set of LA-ICP-MS analyses we analyzed more
Repetition Rate 6 Hz and 10 Hz than 35 major and trace elements in the fluid inclusions from
Spot size 13e31 mm three polished sections (320-1, 320-2 and 320-8). Silicon (as
Carrier gas 0.37 l min1 He an element of the host mineral) was also monitored. Generally,
Ablation duration 20e40 s
Agilent 7900x ICP-MS
the limit of detection (LOD) of the specific elements, as
Sample introduction Ablation aerosol determined by LA-ICP-MS, depends on the inclusion size.
Forward power 1250e1350 W The larger the inclusion, the higher the achievable sensitivity
Ar cooling gas flow rate 15 l min1 and thus the lower calculated LOD. Some elements were
Ar auxiliary gas flow rate 0.75 l min1 consistently around and below the limits of detection. The
Ni sampling cone orifice 1.0 mm
Ni skimmer cone orifice 0.7 mm
number of detected elements was limited in order to improve
Acquisition mode Peak jumping the mass-spectral detection sensitivity of some alkaline,
Channel dwell time 20 ms alkaline-earth, and metal elements. That is why a reduced
Channel per mass 1 menu of only 18 elements (Na, K, Mg, Al, P, Cl, Ca, Mn, Fe,
Measured isotopes Na, K, Mg, Al, P, Cl, Ca, Mn, Ni, Cu, Zn, Rb, Sr, Y, Cs, Ba and Au) was used during the
Fe, Ni, Cu, Zn, Rb, Sr, Y, Cs,
Ba and Au
analyses of fluid inclusions (Table 2). Sodium is the most
Other information abundant cation in the fluid inclusions and its concentration
Gas blank 30 s on-peak zero subtracted can be estimated from fluid inclusion salinities determined by
Washing time 30 s after the laser ended firing microthermometry prior to laser ablation. Its concentration
was used as an internal standard. In Fig. 4, the concentration of
with corresponding salinities of 26.3 wt. % NaCl equiv. The FeO, Zn and Rb become increased when the salinity increases.
total homogenization to liquid occurs at temperatures ranging Especially when the salinity reached the 32 wt. %, these
from 165
C to 170
C. element content remarkably increase. Whereas, the concen-
In the early stage mineralization, S-type inclusions exhibit tration of Cu, Ni, and Sr are increased first and then decreased
two different ways of homogenization. Usually they homog- with increase of salinity content. The content of salt reached
enize by halite disappearance and rarely by bubble disap- 32% also is kick point. The content of Cu and Zn is obviously
pearance. The homogenization temperatures of these decreased.

Table 2
The concentration of 15 trace elements from Fluid inclusions in quartz samples comes from the Hujiayu copper deposit.
405-320-104 405-320-105 405-320-106 405-320-201 405-320-801 405-320-803 405-320-805
Salinity (wt.% NaCl) 26.3 24.3 26.3 35.1 31.8 33.1 32.1
Type L L L S S S S
Ti (
C) 68 68 68
Tm, ice (
C) 32 25 26
Tv (
C) 170 165 161 175 160 112 135
Tm, hal (
C) 243 191 210 190
Th (
C) 243 191 210 190
MgO(wt%) 0.13 0.33 0.20 4.94 0.82 0.60 1.74
Al2O3(wt%) 0.21 0.48 0.08 5.83 0.80 0.63 21.60
P2O5(wt%) 0.19 0.16 0.02 0.00 0.29 0.81 2.67
Cl (ppm) 17,613 19,401 20,552 29,111 23,938 48,876 44,816
K2O (wt%) 4.93 4.60 4.32 21.31 3.71 3.78 5.99
CaO (wt%) 10.5 14.3 14.8 0.6 41 42.4 41.1
MnO (wt%) 3.11 4.11 1.93 0.74 1.68 1.79 2.07
FeO (wt%) 0.03 1.12 0.25 4.96 0.88 1.32 1.33
Ni (ppm) 85.3 37.6 6.1 0.00 72.7 164.8 2022
Cu (ppm) 0.34 0.00 1.59 0.00 239 74.90 439
Zn (ppm) 3163 3051 3044 15,363 1487 2478 2714
Rb (ppm) 372 426 426 1234 159 245 210
Sr (ppm) 3489 3792 3770 1625 8629 17,518 9604
Y (ppm) 1.72 0.20 0.14 0.00 0.58 0.00 6.78
Cs(ppm) 74.9 93.5 96.8 127.6 26.2 43.4 11.2
Ba (ppm) 1649 1790 1821 17,633 3492 9446 5674
Au (ppm) 0.00 6.74 0.00 0.00 0.00 5.85 0.00
12 C.-y. Li et al. / Solid Earth Sciences 3 (2018) 8e15

Fig. 2. Microphotographs of 193 nm laser system ablating spots on quartz.

Fig. 3. Sketch illustrating the fast transient signal obtained from the LA-ICP-MS analysis on an individual inclusion.
 C.-y. Li et al. / Solid Earth Sciences 3 (2018) 8e15
Fig. 4. Diagrams of Cu, Ni, Sr, FeO, Zn, Rb versus salinities.
4. Discussion
4.1. Key technical difficulties for peculiar sample
Fluid inclusions are small relicts of fluid trapped in natural
minerals during their growth from hydrothermal solutions
(primary inclusions), or during later deformation (secondary
inclusions). The content of the inclusion is liberated by drilling
it out of the host mineral using laser ablation, and the aerosol
is transported to the ICP-MS where signals are recorded as
specified in the analytical routine (measurement method).
Therefore, the best host mineral should contain the lowest
trace elements. Quartz is an ideal host mineral (Pettke et al.,
2012). The absorbance of the laser beam by the host mineral
and the fluid inclusion phases depends on the laser wavelength
and needs to be maximized to allow for well controlled dril-
ling through the host mineral and ablation of the fluid inclu-
sion content. Because of the quartz belonging to transparent
mineral, this is achieved by the use of short-wave UV radiation
(193e213 nm) (Allan et al., 2005; Gunther et al., 1998; Leisen
et al., 2012; Pettke et al., 2012; Shepherd and Chenery, 1995).
The aim of ablation is to liberate the entire fluid inclusion
content (avoiding any loss during ablation) and to produce a
transient fluid inclusion signal that can be correctly recorded
by the mass spectrometer. While this is simple in principle, it
is often difficult to achieve in practice. Importantly, the abla-
tion quality of quartz varies significantly. It has so far not been
possible to link this diverse behavior to specific analytical
13
parameters (Pettke et al., 2012). In order to achieve the best
working conditions, the clean quartz grains were analyzed
dozens of times, using different laser energy densities and
repetition rates (Fig. 2). We found that, for our laser ablation
system, a relatively high energy density between 20 and 25 J/
cm2 on the sample surface is required. Some quartz has the
fissuring which can cause the quartz exploding. Lager diam-
eter of the spot means more fissuring of quartz. When quartz
exploded during the ablation process which is in an uncon-
trolled manner, an unconstrained fraction of the inclusion
content is lost, rendering lower quality of the analysis. To
obtain adequate results (Fig. 3), we suggest laser energy
density is 25 J/cm2, laser pulse repetition rates are commonly
between 6 and 10 Hz, and the laser beam should be larger than
the largest diameter of the inclusion to ensure complete
ablation for inclusions with daughter minerals.
4.2. Calibration and calculation of element
concentrations
23
Na is generally used as an internal standard for LA-ICP-
MS analysis of fluid inclusions (Allan et al., 2005; Heinrich
et al., 2003; Sun et al., 2016) and Cl has also been used by
some workers (Stoffell et al., 2004, 2008; Wilkinson et al.,
2009). However, the high first ionization energy of chlorine
results in weak signal intensities. Analysis of halogens by LA-
ICP-MS is not a standard practice, as halogens tend to have
relatively low ionisation efficiencies that lead to lower analyte
14 C.-y. Li et al. / Solid Earth Sciences 3 (2018) 8e15
sensitivity, and thus increased detection limits. The energy
required to positively ionise fluorine (17.42 eV) makes it
impossible for quantification via an Ar (ionisation energy:
15.76 eV) plasma typically used in LA-ICP-MS systems.
Bromine, Cl and I are not yet routinely measured by LA-ICP-
MS, not only because of their high ionisation energies (Cl:
12.97 eV, Br: 11.81 eV, and I: 10.45 eV), but also because of
the lack of suitable standard materials for these elements.
Furthermore, the 35Cl (the most abundant isotope) has a high
background relative to the weak signal obtained. Chlorine has
two stable isotopes 35Cl (75.78%) and 37Cl (24.22%). The
masses of the Cl are therefore very close to stable isotopes of
Ar (36Ar and 38Ar). Because Ar is so abundant in the plasma of
the ICP-MS, peak tailing of 36Ar and 38Ar has the potential to
cause interference on 35Cl and 37Cl.
For this LA-ICP-MS analysis, the intensity of the 35Cl
signal is three orders of magnitude less intense than the in-
tensity of the 23Na signal. Uncertainty on 35Cl content is
around 40% when it is measured by LA-ICP-MS. Because the
uncertainties on the 23Na of microthermometric estimation for
ice melting, hydrate melting, halite dissolution in these dia-
grams are unknown, the uncertainty on 23Na concentration is
taken as 20%, 30% by default, which is far below 40% (un-
certainty for 35Cl measured by LA-ICP-MS). Nevertheless, it
is still a useful reference for fluid inclusion analyses.
5. Conclusion
Laser ablation inductively coupled plasma mass spectrom-
etry (LA-ICP-MS) is a powerful tool for in situ analysis of in-
dividual fluid inclusions. Both 23Na and 35Cl may be used as
internal standards. NIST SRM glasses are used as an external
standard. For our analyses, the intensity of the 35Cl signal is
three orders of magnitude less intense than the intensity of the
23
Na signal, such that has larger errors. For the RESOlution S-
155 laser system, the optimal energy density ranges between 20
and 25 J/cm2, with repetition rates of 6e10 Hz.
Acknowledgement
This study is supported by the National Natural Science
Foundation of China (No. 41403034) and MOST of China
2016YFC0600408, CAS XDB18020000.
References
Allan, M.M., Morrison, G.W., Yardley, B.W.D., 2011. Physicochemical evo-
lution of a porphyry-breccia system: a laser ablation ICP-MS study of fluid
inclusions in the Mount Leyshon Au Deposit, Queensland, Australia. Econ.
Geol. 106, 413e436.
Allan, M.M., Yardley, B.W.D., Forbes, L.J., Shmulovich, K.I., Banks, D.A.,
Shepherd, T.J., 2005. Validation of LA-ICP-MS fluid inclusion analysis
with synthetic fluid inclusions. Am. Mineral. 90, 1767e1775.
Audetat, A., Gunther, D., Heinrich, C.A., 1998. Formation of a magmatic-
hydrothermal ore deposit: insights with LA-ICP-MS analysis of fluid in-
clusions. Science 279, 2091e2094.
Audetat, A., Gunther, D., Heinrich, C.A., 2000a. Causes for large-scale metal
zonation around mineralized plutons: fluid inclusion LA-ICP-MS evidence
from the Mole Granite, Australia. Econ. Geol. 95, 1563e1581.
Audetat, A., Gunther, D., Heinrich, C.A., 2000b. Magmatic-hydrothermal
evolution in a fractionating granite: a microchemical study of the Sn-W-F-
mineralized Mole Granite (Australia). Geochem. Cosmochim. Acta 64,
3373e3393.
Audetat, A., Pettke, T., 2003. The magmatic-hydrothermal evolution of two
barren granites: a melt and fluid inclusion study of the Rito del Medio and
Canada Pinabete plutons in northern New Mexico (USA). Geochem.
Cosmochim. Acta 67, 97e121.
Audetat, A., Pettke, T., Heinrich, C.A., Bodnar, R.J., 2008. The composition of
magmatic-hydrothermal fluids in barren and mineralized intrusions. Econ.
Geol. 103, 877e908.
Chi, G.X., Ni, P., 2007. Equations for calculation of NaCl/(NaCLþCaCl2)
ratios and salinities from hydrohalite-melting and ice-melting temperatures
in the H2O-NaCl-CaCl2 system. Acta Petrol. Sin. 23, 33e37.
Guillong, M., Latkoczy, C., Seo, J.H., Gunther, D., Heinrich, C.A., 2008.
Determination of sulfur in fluid inclusions by laser ablation ICP-MS.
J. Anal. Atomic Spectrom. 23, 1581e1589.
Gunther, D., Audetat, A., Frischknecht, R., Heinrich, C.A., 1998. Quantitative
analysis of major, minor and trace elements in fluid inclusions using laser
ablation inductively coupled plasma mass spectrometry. J. Anal. Atomic
Spectrom. 13, 263e270.
Heinrich, C.A., Gunther, D., Audetat, A., Ulrich, T., Frischknecht, R., 1999.
Metal fractionation between magmatic brine and vapor, determined by
microanalysis of fluid inclusions. Geology 27, 755e758.
Heinrich, C.A., Pettke, T., Halter, W.E., Aigner-Torres, M., Audetat, A.,
Gunther, D., Hattendorf, B., Bleiner, D., Guillong, M., Horn, I., 2003.
Quantitative multi-element analysis of minerals, fluid and melt inclusions
by laser-ablation inductively-coupled-plasma mass-spectrometry. Geo-
chem. Cosmochim. Acta 67, 3473e3497.
Jiang, Y.H., Niu, H.C., Bao, Z.W., Li, N.B., Shan, Q., Yang, W.B., Yan, S.,
2014. Fluid evolution of the Paleoproterozoic Hujiayu copper deposit in
the Zhongtiaoshan region: evidence from fluid inclusions and carbon-
oxygen isotopes. Precambrian Res. 255, 734e747.
Leisen, M., Dubessy, J., Boiron, M.C., Lach, P., 2012. Improvement of the
determination of element concentrations in quartz-hosted fluid inclusions
by LA-ICP-MS and Pitzer thermodynamic modeling of ice melting tem-
perature. Geochem. Cosmochim. Acta 90, 110e125.
Li, C.Y., Zhang, H., Wang, F.Y., Liu, J.Q., Sun, Y.L., Hao, X.L., Li, Y.L.,
Sun, W.D., 2012. The formation of the Dabaoshan porphyry molybdenum
deposit induced by slab rollback. Lithos 150, 101e110.
Lin, J., Liu, Y.S., Yang, Y.H., Hu, Z.C., 2016. Calibration and correction of
LA-ICP-MS and LA-MC-ICP-MS analyses for element contents and iso-
topic ratios. Solid Earth Sci. 1, 5e27.
Oakes, C.S., Bodnar, R.J., Simonson, J.M., 1990. The system Nacl-Cacl2-H2o
.1. The ice liquidus at 1 atm total pressure. Geochem. Cosmochim. Acta
54, 603e610.
Pettke, T., Oberli, F., Audetat, A., Guillong, M., Simon, A.C., Hanley, J.J.,
Klemm, L.M., 2012. Recent developments in element concentration and
isotope ratio analysis of individual fluid inclusions by laser ablation single
and multiple collector ICP-MS. Ore Geol. Rev. 44, 10e38.
Pique, A., Canals, A., Grandia, F., Banks, D.A., 2008. Mesozoic fluorite veins
in NE Spain record regional base metal-rich brine circulation through
basin and basement during extensional events. Chem. Geol. 257,
139e152.
Richard, A., Pettke, T., Cathelineau, M., Boiron, M.C., Mercadier, J.,
Cuney, M., Derome, D., 2010. Brine-rock interaction in the Athabasca
basement (McArthur River U deposit, Canada): consequences for fluid
chemistry and uranium uptake. Terra. Nova 22, 303e308.
Seo, J.H., Guillong, M., Heinrich, C.A., 2009. Role of sulfur in hydrothermal
metal fractionation and the formation of porphyry-type ore deposits.
Geochem. Cosmochim. Acta 73. A1197eA1197.
Shepherd, T.J., Chenery, S.R., 1995. Laser-ablation ICP-MS elemental anal-
ysis of individual fluid inclusions - an evaluation study. Geochem. Cos-
mochim. Acta 59, 3997e4007.
Stoffell, B., Appold, M.S., Wilkinson, J.J., McClean, N.A., Jeffries, T.E., 2008.
Geochemistry and evolution of Mississippi valley-type mineralizing brines
from the Tri-State and Northern Arkansas districts determined by LA-ICP-
MS microanalysis of fluid inclusions. Econ. Geol. 103, 1411e1435.
 C.-y. Li et al. / Solid Earth Sciences 3 (2018) 8e15
Stoffell, B., Wilkinson, J.J., Jeffries, T.E., 2004. Metal transport and deposition
in hydrothermal veins revealed by 213nm UV laser ablation microanalysis
of single fluid inclusions. Am. J. Sci. 304, 533e557.
Sun, D.Z., Hu, W.X., 1993. Precambrian Geochronology, Chronotectonic
Frameworkand Model of Chronocrustal Structure of the Zhongtiao
Mountains. Geological publishing house, Beijing.
Sun, W.D., Zhang, L.P., Guo, J., Li, C.Y., Jiang, Y.H., Zartman, R.E.,
Zhang, Z.F., 2016. Origin of the mysterious Yin-Shang bronzes in China
indicated by lead isotopes. Sci. Rep. 6.
Tu, X.L., Zhang, H., Deng, W.F., Ling, M.X., Liang, H.Y., Liu, Y., Sun, W.D.,
2011. Application of RESOlution in-situ laser ablation ICP-MS in trace
element analyses. Geochemical 40, 83e98 (in Chinese).
Ulrich, T., Gunther, D., Heinrich, C.A., 1999. Gold concentrations of
magmatic brines and the metal budget of porphyry copper deposits. Nature
399, 676e679.
15
Ulrich, T., Gunther, D., Heinrich, C.A., 2002. Evolution of a porphyry
Cu-Au deposit, based on LA-ICP-MS analysis of fluid inclusions: Bajo
de la Alumbrera, Argentina (vol. 96, pg 1743, 2001). Econ. Geol. 97,
1889e1920.
Ulrich, T., Mavrogenes, J., 2008. An experimental study of the solubility of
molybdenum in H2O and KCl-H(2)O solutions from 500 degrees C to 800
degrees C, and 150 to 300 MPa. Geochem. Cosmochim. Acta 72, 2316e2330.
Wei, D.Y., Xing, S.C., Liang, X., 1984. The implications of the Hu-Bi type
copper deposits in the Zhongtiaoshan region. Acta Hebei Geol. Coll.
30e41 (in Chinese).
Wilkinson, J.J., Stoffell, B., Wilkinson, C.C., Jeffries, T.E., Appold, M.S.,
2009. Anomalously metal-rich fluids form hydrothermal ore deposits.
Science 323, 764e767.