Chemical Geology 529 (2019) 119326

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Chemical Geology
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Bulk microanalysis of assemblages of small fluid inclusions by LA-ICP-MS: T

Methodology and application to orogenic gold systems
⁎
Györgyi Tubaa, , Daniel J. Kontaka, Zoltán Zajaczb,1, Joseph A. Petrusa
a
Mineral Exploration Research Centre, Harquail School of Earth Sciences, Laurentian University, 935 Ramsey Lake Road, Sudbury, ON, P3E 2C6, Canada
b
Department of Earth Sciences, University of Toronto, 22 Russell Street, Toronto, ON, M5S 3B1, Canada

A R T I C LE I N FO A B S T R A C T

Editor: Balz Kamber Microanalysis of individual fluid inclusions by laser ablation inductively coupled mass spectrometry (LA-ICP-
Keywords: MS) is a powerful tool for reconstructing the composition of hydrothermal fluids, but it demands a sample
Fluid inclusions quality that is unattainable in many cases. In orogenic gold deposits, the need for direct fluid microanalysis has
LA-ICP-MS been present for several decades, but due to the high fluid flux and prolonged hydrothermal and tectonic history
Fluid chemistry that typifies these systems, most samples do not meet the criteria of fluid inclusion size and distribution that
Orogenic allow LA-ICP-MS analysis of individual isolated fluid inclusions. To overcome this difficulty, a method has been
Gold deposits developed and tested, whereby areas of quartz densely populated with fluid inclusions (e.g., growth zones,
secondary planes) are analyzed along a single continuous laser ablation profile; the generated signals are sub-
sequently converted to time-slice datasets and plotted as element ratios in ternary diagrams to reconstruct
specific major- and trace-element ratios. The estimated fluid compositions are in good agreement with previous
analytical results of the same material (microthermometry, evaporate mound and conventional LA-ICP-MS) and
are shown to be geologically viable on a boarder scale when compared to literature data from similar ore
environments. The method has high spatial and chemical resolution, which allows the reconstruction of micro-
scale fluid chemical changes, such as significant fluctuation in the relative element concentration (e.g., K, Rb, Ba,
Sr and V versus Na, Li and As) during crystal growth, as observed in one of the test samples. The significance of
this bulk LA protocol is that it allows the quick, easy and cost-effective microanalysis of samples that are ty-
pically inundated with fluid inclusions, such as those in orogenic and epithermal systems, which would other-
wise not be amenable for further quantitative analysis to constrain fluid chemistry.

1. Introduction contaminating the target volume by accidentally breaching nearby in-

In situ LA-ICP-MS (laser ablation inductively coupled mass spec-
trometry) analysis of individual fluid inclusions (FI) has been shown to
be an effective method for directly determining fluid chemistry in fossil
hydrothermal systems (e.g., Audétat et al., 1998; Günther et al., 1998).
The method has been widely applied and become essential for advan-
cing our understanding of fluid evolution and metal transport in several
ore systems: in particular porphyry Cu (e.g., Heinrich et al., 1999;
Ulrich et al., 2002; Williams-Jones and Heinrich, 2005; Landtwing
et al., 2005), but also Sn-W (Audétat et al., 2000) and orogenic gold
(Garofalo et al., 2014; Morales et al., 2016; Fusswinkel et al., 2017)
deposits. An inevitable limitation of this method, however, is that it
requires relatively large (> 10 μm) and isolated FIs to prevent
clusions and thus generating a mixed signal. The latter requirement is
very rarely fulfilled in samples from some ore deposit settings, in par-
ticular orogenic gold deposits, where the quartz host, most often than
not, is densely populated by multiple superimposed assemblages of
small (typically 2–7 μm or less) FIs (Fig. 1). Other cases where such
small, densely populated FIs occur are in epizonal settings where it is
not uncommon to find primary growth surfaces of minerals inundated
with FIs (e.g., Bodnar et al., 1985). This issue severely limits the
availability of suitable material for in situ LA-ICP-MS analysis of single
FIs and thus providing the essential fluid chemistry for some ore deposit
types.
Fluid inclusion microthermometric studies generally only provide
limited and approximate compositional data (i.e., XCO2, wt.% equiv.

⁎
Corresponding author.
E-mail address: gtuba@laurentian.ca (G. Tuba).
1
Present address: Mineral Resources and Geofluids, Section of Earth and Environmental Sciences, University of Geneva, 13 Rue des Maraîchers, 1205 Geneva,
Switzerland.

https://doi.org/10.1016/j.chemgeo.2019.119326
Received 15 March 2019; Received in revised form 29 September 2019; Accepted 3 October 2019
Available online 14 October 2019
0009-2541/ © 2019 Elsevier B.V. All rights reserved.
G. Tuba, et al.
NaCl, major cation ratios; Roedder, 1984; Bodnar and Vityk, 1994;
Bodnar et al., 2014). Consequently, despite several decades of research
and numerous studies, such work has not contributed significantly new
information and thus has limited advancing our understanding of the
nature of orogenic fluids implicated in gold formation (see Bodnar
et al., 2014 for summary). Whereas evaporate mound SEM-EDS analysis
(Kontak, 2004) provides the means to at least semi-quantitatively de-
termine major- and minor-element chemistry (e.g., Kontak and Kyser,
2011; Kontak and Tuba, 2017, 2018), such analysis does not allow the
characterization of fluids on the trace-element level or the character-
ization of individual inclusions with certainty. Similarly, whereas
crush-leach methods provide quantitative chemical data to low detec-
tion limits (Banks and Yardley, 1992; Gleeson, 2003), they have the
shortcoming of lack of resolution and the averaging of FI populations.
An alternative approach is needed in order to advance further the da-
tabase of fluid chemistry in different ore-deposit systems.
This paper provides a summary and preliminary results of a new
protocol which addresses the issues above: a complementary method to
traditional LA-ICP-MS analysis of FIs that provides semi-quantitative
chemical data for ore forming fluids trapped in minute, densely spaced
inclusions. We address this by first describing the theoretical approach,
protocol and sampling, analytical parameters and then provide results
for two contrasting gold-deposit settings in the Archean Abitibi green-
stone belt, Canada.
2. Theory of the method
The concept of using laser ablation for fluid inclusion analysis
emerged not long after the LA-ICP-MS method itself became an ac-
knowledged micro-analytical method (e.g., Shepherd and Chenery,
1995; Ghazi et al., 1996; Moissette et al., 1996; Audétat et al., 1998;
Günther et al., 1998; Heinrich et al., 1999). The method involves the
sampling of individual fluid inclusions by a focused laser beam that
bores into the mineral host, breaches the inclusion and ablates the
contained solid and/or fluid material, which is then transported from
2
Chemical Geology 529 (2019) 119326
Fig. 1. Examples of typical orogenic vein
samples from the Archean Abitibi greenstone
belt inundated by secondary (a, b) and primary
(c, d, e) FIs. Laser ablation ICP-MS analysis of
individual FIs is precluded by the abundance of
FIs in such samples. (a) Abundant subparallel
planes of decrepitated FIs reflecting post-en-
trapment ductile deformation; sample from
Black Fox deposit. (b) High abundance of sec-
ondary FIs reflecting increased fluid flux in an
area of high fracture density (outlined by white
dashed line; Bell Creek deposit). (c–e) Densely
packed FIs outlining primary growth zones in
drusy quartz. The area highlighted in Fig. 1c is
enlarged in Fig. 1d; samples from the Ashley (c,
d) and Kirkland Lake (e) deposits.
the sample chamber to the ICP-MS by an Ar or He carrier gas. Absolute
element concentrations are calculated after subtracting the gas and
matrix backgrounds and standardizing the fluid chemical signature
against Na, which can be predetermined for each inclusion by using
salinity estimates obtained by microthermometry. The method requires
analyte FIs that are relatively isolated (to avoid breaching surrounding
inclusions) and large enough (> 10 μm) to produce reliable quantita-
tive data by adequate signal to background ratio (Gagnon et al., 2003).
Typical examples of orogenic vein quartz are very rarely suitable for
the analysis of individual inclusions. These samples are inundated with
FIs, which merely reflects the nature of these systems: extended ex-
posure to hydrothermal fluids and periods of deformation. In such si-
tuations, the high abundance of FIs warrants that LA-ICP-MS analysis of
the host should result in a mixed chemical signal that reflects varying
proportions of the quartz matrix and contained FIs. In theory, therefore,
processing of such signals should generate chemical data about the fluid
composition if the abundance of inclusions is high enough in the unit
volume of quartz. The composition of fluid in this theoretical mixed
signal, however, will be an average of all the (potentially different)
fluid inclusion assemblages (FIA) present. In this case, the value of such
information would be considered modest, thus the method has to have
the resolution (either spatial or statistical) to distinguish among che-
mical subgroups.
In order to address the above, we have designed a series of tests
using the classic LA-ICP-MS method with a different approach. Here we
use laser scanning along a line path to acquire a chemical profile across
areas in quartz that are densely populated with FIs and then process the
element signals into a time-slice dataset (TSD), where each data point
represents one complete analysis of the selected element list (i.e., one
sweep of the MS; e.g., Gourcerol et al., 2018). The rationale behind this
type of acquisition follows:
(1) Spatial resolution and visual proofing. The nature and diversity of
the FIA to be analyzed can be visually established before analysis and
the TSD spatially matched to that, which allows one to track variations
in chemical composition as a function of the FIA population(s).
G. Tuba, et al.
Potential contamination (e.g., epoxy in cracks, solid inclusions in
quartz, etc.) can be verified visually and addressed.
(2) Acquiring statistically robust data. Unlike analyzing an individual
FI via breaching and complete extraction of a single inclusion volume,
this method uses relatively fast ablation of multiple FIs which may
result in highly variable individual readings for mechanical reasons
(e.g., partial ablation of individual inclusions). By acquiring and plot-
ting the individual data points extracted from the TSD, we generate a
large database where clustering of results in confined compositional
space would be considered to represent a meaningful chemical signal
and haloes (i.e., outliers) would be plausibly attributed to contamina-
tion, such as solid inclusions in quartz.
Among the theoretical limitations of the method, a significant one is
the lack of absolute concentrations in ppm. To calculate concentration
data, Si can be used as an internal standard (46.74 wt.% for quartz), as
the quartz matrix is always present in the analysis, but that in itself
skews the data since the quartz:fluid, and therefore the Si:Na, ratio is
constantly changing as the beam traverses across variably inclusion-
populated areas. Another possible limitation is that the elemental
concentration in a given reading depends on both the volume of FI
material analyzed and its composition, generally expressed as the in-
clusion salinity. Working with element ratios can, however, eliminate
this problem (e.g., Samson et al., 2008) and may render chemical sub-
groups, if present, distinguishable. This approach is also necessary be-
cause of the lack of a fluid-representative internal standard (e.g., Na)
that is based on previous microthermometric measurements of the ab-
lated inclusions. The FIs primarily targeted in this study are those that
are extremely challenging and time-consuming or impossible to carry
out microthermometry on because of the minute size and the limita-
tions on visual observations arising from that. In such inclusions, pre-
cise registration of phase changes that would allow an approximation of
salinity and cation composition hinders using Na as an internal stan-
dard. Using element ratios without the need of such standard also al-
lows a quick and effective identification and chemical characterization
of distinct fluid groups (i.e., FIA).
Expressing the fluid chemistry as element ratios also has the ad-
vantage of eliminating the problem of partial ablation of FIs. Partial
ablation is unavoidable with this method as the laser beam targets an
area with multiple FIs as opposed to a single, isolated object, and
opening of additional inclusions in the damage zone around the laser
trace is very probable. The contribution of these partially opened in-
clusions to the signal may raise the absolute concentrations, but in-
asmuch as the FIA is homogeneous and the analyzed elements are
contained in a single phase in the inclusions (i.e., in the aqueous
component with no daughter phases), the ratio of these elements will
not be affected. If daughter minerals are left behind in the FI cavity
during partial ablation, the escaping fluid phase represents neither the
whole FI nor the original element ratios, and it may affect the analytical
results depending on the size of the damage zone (and, thus, the relative
amount of elements contributed by partially ablated heterogeneous
FIs).
3. Protocol and sampling
The first phase of the study was designed to assess if the approach
itself was viable and to determine what fundamental sample require-
ments were necessary to ensure the generation of high quality, mean-
ingful data. The main questions addressed were: (1) the detectability
and robustness of signals coming from FIs, (2) the viability and (3) the
reproducibility of the generated data, and (4) the optimal instrumental
conditions.
For the initial testing of the method, two samples with contrasting
attributes were used in the experiments. The first sample (GF-185) is a
gold-bearing, crustiform quartz-carbonate vein from the Archean Grey
Fox orogenic gold deposit (Ontario, Canada) (Fig. 2). The sample con-
tains euhedral, coarse-grained (up to 1 cm) quartz (Fig. 2a, b) with a
3
Chemical Geology 529 (2019) 119326
relatively simple fluid inclusion record. Primary FIAs present along
densely-packed growth zones (Fig. 2c, d) have a moderate-salinity (avg.
7.1 wt.% NaCl equiv.), NaCl-K(-Ca?) aqueous fluid based on first and
last ice melting temperatures (Te -26.8 to -22.6 °C and Tmice -5.3 to
-3.7 °C, respectively), whereas cross-cutting secondary FIAs (Fig. 2b, e)
represent several generations of NaCl-K(-Ca?) aqueous fluids with
variable salinities (3.9 to 19.1 wt.% NaCl equiv.), again based on first
and last ice melting (Te < -26.5 °C and Tmice between -15.6 and -2.3 °C,
respectively). The lower first melting temperature of the secondary
population as compared to primary FIAs may indicate higher amounts
of additional, possibly divalent, cations to Na and K (Steele-MacInnis
et al., 2016). Both types of inclusions are typically ≤2 μm in diameter
and are therefore unsuitable for being ablated and analyzed in-
dividually using LA-ICP-MS. The areas selected for the experiment ex-
hibit several growth zones representing a single primary FIA with high
(typically 6 to 10 vol% in any unit volume of quartz) FI abundance and
are essentially devoid of secondary FIAs. Primary FIs have a generally
homogeneous 3D distribution and size within the individual growth
zones, warranting in theory a relatively constant fluid:matrix ratio in
each sweep of the laser analysis. Occasional secondary FIAs are ob-
served along fluid inclusion planes (FIP) in quartz sections otherwise
devoid of primary FIAs; the fluid:matrix ratio in these areas depends on
the orientation of the FIP relative to the laser path, and therefore may
vary greatly from sweep to sweep. Sample GF-185 was also used to test
viability and reproducibility of data using different instrumental set-
tings.
The second sample (144Gap) is a mineralized Archean orogenic
quartz vein from the 144 Gap zone at Timmins West (Ontario, Canada)
(Fig. 3). The area selected for analysis hosts three types of secondary
inclusions: carbonic, aqueous-carbonic and aqueous inclusions (Fig. 3b
to e). Based on our microthermometric and LA data of similar FIAs from
the 144 Gap zone, the fluids are of NaCl-CaCl2 (aqueous-carbonic) and
NaCl-KCl-CaCl2 (aqueous) composition with moderate (ca. 6 wt.% NaCl
equiv.) to high (ca. 24 wt.% NaCl equiv.) salinity, respectively. In the
sample used for the study, FIPs are relatively isolated in a FI-poor, clear
area of quartz (Fig. 3a). The 2D distribution of FIs along the selected FIP
was relatively homogeneous but the size of FIs within the FIAs varied
from 1 to 10 μm. All selected FIPs had a subvertical orientation to the
sample surface to maximize the fluid:matrix ratio during analysis.
These FIAs were used to test the viability and spread of data acquired at
relatively low (ca. 2 vol%) fluid:matrix ratios and to test whether che-
mical contrasts between the individual FIPs could be detected.
In both of the samples described, FI-free areas of quartz were also
analyzed by means of spot analysis to determine the composition of the
host quartz.
4. Analytical and data processing methods
Approximate fluid:matrix ratios in the selected samples were de-
termined from multifocal photomicrographs using the image analysis
software ImageJ (Schindelin et al., 2015).
Laser ablation ICP-MS analyses were carried out at the Magmatic
and Ore-Forming Processes Research Laboratory at the University of
Toronto (Canada), on a system comprising an NWR-193 UC excimer
laser ablation system and an Agilent 7900 quadrupole mass spectro-
meter. The instrument was tuned to robust plasma conditions indicated
by near equal sensitivity for Th and U; ThO production rates of < 0.3%
and doubly charged ion production rate < 0.35% (monitored using
42
Ca/Mass 21 ratios). The laser was operated at 10 Hz repetition rate
with 12 J/cm2 energy density on the sample surface in all runs.
Analyzed isotopes are 7Li, 11B, 23Na, 25Mg, 27Al, 29Si29, 34S, 35Cl, 39K,
44
Ca, 49Ti, 51V, 55Mn, 56Fe, 59Co, 62Ni, 65Cu, 66Zn, 75As, 79Br, 85Rb, 88Sr,
107
Ag, 118Sn, 121Sb, 133Cs, 137Ba, 140Ce, 182W, 197Au, 208Pb and 209Bi.
The dwell time for all the elements was 10 ms, except for Au (30 ms),
adding up to a total sweep time of 402 ms (including 2 ms quadrupole
settling between each mass). Feed time of the system was ca. 1 s; a glass
G. Tuba, et al.
mixing device for He and auxiliary Ar with about 20 cm3 internal vo-
lume was used in which the turbulent flow partially averages about 2–3
sweep-worth of ablated aerosol out. Line profiles were acquired by a
rectangular laser beam (26 × 26 to 100 × 100 μm) with lateral scan-
ning speed of the stage between 2 and 13 μm/s (Table 1). Beam size for
square spot analysis of visually FI-free quartz varied between 50 × 50
to 100 × 100 μm. The NIST SRM 610 silicate glass was used as an ex-
ternal standard and was measured twice at the beginning and end of
each analysis block to allow for drift correction. To improve counting
4
Chemical Geology 529 (2019) 119326
Fig. 2. Petrographic features of FIs observed in
sample GF-185 from the Grey Fox deposit. (a)
Crustiform vein texture with abundant primary
FIs defining growth zones in quartz (qtz) and
carbonate (carb) vein fill. (b) Representative
vein sample showing typical appearances of
FIAs. Primary (p) inclusions are located in
growth zones (highlighted area), whereas
pseudosecondary (ps) and secondary (sec) FIs
are associated with healed fractures either
confined within a single grain (ps) or cutting
grain boundaries (sec). (c) Primary FIs in-
undating the outer growth zone of quartz that
shows commonly observed radial texture with
the long axis parallel to growth direction (cf.
Bodnar et al., 1985). (d) Primary aqueous FIs
in quartz growth zone. Although abundant, the
FIs are very small, usually below 2 μm. The
opaque areas are decrepitated FI cavities at or
near the sample surface. (c) Trails of secondary
aqueous FIs defining healed fracture planes.
These FIs are significantly less abundant than
primary FIs, but are of similar size.
statistics, 44Ca rather than 43Ca was detected keeping in mind the low
oxide production rates at our regular analytical conditions. Never-
theless, correction for the interference of 28Si16O with 44Ca was applied
based on direct determination of the 44Ca/29Si = 0.00020 by ablating
pure SiO2 glass at our regular tuning parameters. The artificial 44Ca
signal corresponds to about 30–50 ppm Ca in the quartz before cor-
rection. The error on the correction due to intraday change of the oxide
production rates is estimated to correspond to 10–20 ppm artificial Ca
in the quartz. The raw data were processed by Iolite v3.6 (Paton et al.,
Fig. 3. Petrographic features of FIs observed in
sample 144Gap from the Gap zone deposit.
Note that all FIAs observed are of secondary
origin. (a) Coarse-grained quartz from vein
cutting syenitic host (syn). Note that the vein
quartz exhibits areas both inundated and rela-
tively barren of secondary FIPs. Laser ablation
analysis targeted well-isolated secondary FIPs
in the relatively FI-poor areas to avoid the
presence of multiple FIAs in the same ablation
volume. (b) Plane of aqueous FIA used for the
LA profile a26 in Fig. 8a. (c) A modified FIA
with heterogeneous aqueous-carbonic FIs (LA
profile a29 in Fig. 8a). (d) A FIA with homo-
geneous aqueous-carbonic FIs (profile a36 in
Fig. 8a). (e) A FIA of single-phase carbonic FIs
(part of profile a38 in Fig. 8a).
G. Tuba, et al. Chemical Geology 529 (2019) 119326

Table 1
Summary of instrumental settings for line and spot analyses.
Profile Target Analysis type Scan geometry Signal collection time1 Beam size Scanning speed Number of laser pulses / spot Depth of ablation2

GF-185
a03 growth zone line across zones 145 s 50 × 50 μm 3 μm/s 167 60 μm
a04 growth zone line across zones 77 s 50 × 50 μm 5 μm/s 100 50 μm
a05 growth zone line across zones 170 s 50 × 50 μm 2 μm/s 250 70 μm
a07 growth zone line across zones 294 s 50 × 50 μm 3 μm/s 167 60 μm
a08 growth zone line across zones 72 s 26 × 26 μm 13 μm/s 20 20 μm
a18 growth zone line across zones 486 s 50 × 50 μm 3 μm/s 167 60 μm
a21 growth zone line across zones 530 s 50 × 50 μm 3 μm/s 167 60 μm
a22 quartz spot 17 s 100 × 100 μm
a23 quartz spot 44 s 60 × 60 μm
a24 quartz spot 32 s 60 × 60 μm
144Gap
a26 secondary FIP line along FIP 386 s 60 × 60 μm 2 μm/s 300 100 μm
a27 quartz spot 53 s 60 × 60 μm
a28 quartz spot 47 s 60 × 60 μm
a29 secondary FIP line along FIP 431 s 70 × 50 μm 3 μm/s 233 80 μm
a34 secondary FIP line along FIP 329 s 50 × 50 μm 3 μm/s 167 70 μm
a35 quartz spot 51 s 60 × 60 μm
a36 secondary FIP line along FIP 483 s 50 × 50 μm 3 μm/s 167 70 μm
a37 quartz spot 48 s 50 × 50 μm
a38 secondary FIP line across FIP 748 s 50 × 50 μm 2 μm/s 250 100 μm
a39 quartz spot 48 s 50 × 50 μm

1
Collection of gas blank not included.
2
Measured post experiment. All spot analyses ablated through the 120-μm thick quartz wafer.

2011) using the trace elements data reduction scheme (Woodhead
et al., 2007) and Si (46.7 wt. %) as the internal reference. Note that
although an internal standard was used, the data are still considered
semi-quantitative. The time resolved semi-quantitative data were ex-
ported from Iolite and further processed in the geochemical data ana-
lysis software ioGAS. Raw and TSD processed data are given in Table
A1 and Table A2, respectively.
As Fig. 4 demonstrates, the raw time-resolved LA signals closely
mirror changes in FI abundance during acquisition, and are suitable for
further studies. After acquisition and processing, data were handled in
the same manner for all line profiles. For visual verification, the TSD of
selected elements representing the contained fluid were plotted on
elapsed time versus concentration diagrams and then matched to the
photomicrographs showing the trace of line analyses by lining up the
respective endpoints of the line diagram (excluding signals for gas
blank and epoxy, if present) and the laser trace. Areas of major visual
contrasts (i.e., growth zones with variable FIA abundances in GF-185
and the presence or absence of FIAs in 144Gap) were distinguished in
the photomicrograph and data points of the matching TSD sections
assigned into data groups by using the data selection feature of ioGAS,
where processing and plotting of all data groups were carried out as
well.
Spot analyses of relatively inclusion-free quartz was gathered to
establish the background, but instead of calculating a single bulk
composition for the spots, data were processed as TSD to get a “depth
profile” in the selected areas. This means of data processing is necessary
because FIs in these samples are typically so abundant that their acci-
dental analysis cannot be avoided as the laser drills deeper into the
grain, even if the analyzed area appears to be relatively inclusion-free
on the surface. In such cases, even a small amount of FIs can raise the
level of “fluid-indicator” elements (e.g., Na, K) in the analyses. By
looking at the TSD data, those contaminating parts can be discarded
and the rest of the analysis plotted as a data cloud, similarly to the line
profile data, to get the quartz background for future reference.
Calculated TSD data of profile and quartz spot analyses were com-
pared to establish which elements have higher affinity to FI-rich areas,
i.e., which ones can be regarded as indicative for fluid composition in
the mixed signals. Aluminum values were found to increase sig-
nificantly and unrealistically in the FI-rich zones of GF-185 (cf. Table
A1 and Table A2) and were confirmed by means of CL imagery to have
been caused by submicron grains of the gamma-alumina polishing
agent collecting in the opened FI pits on the sample surface. Aluminum
values, therefore, were disregarded from further studies. Sample GF-
185 also contains pyrite and native gold in the vein assemblage, and a
spike at the start of Fe, Pb and more rarely As signals in some profiles
suggest possible smearing of these on the sample surface that may raise
the measured absolute concentrations of these elements.
5. Analytical results
5.1. High fluid:matrix ratio profiles
Seven line profiles across variably inundated growth zones and
three spot analyses from FI-free areas of quartz were collected from
sample GF-185 (Figs. 5–7). In all cases, the TSD profile diagrams lined
up very well with the traces of the line profiles visually and the to-
pology of certain element concentrations typical of fluid inclusions (e.g.,
Na, K; see Figs. 5b and 7 b) closely follow the changes from FI-domi-
nated zones to quartz-dominated areas, indicating that the fluid sig-
nature is reflected by the signal at the detector. Element concentrations
in profile segments with high and relatively constant fluid:matrix ratios
(i.e., primary FIA in growth zones) were selected and compared to those
in quartz spot analyses (Fig. 8). Based on their general abundance and
affinity to either the quartz matrix or the FI-rich areas, three element
groups can be distinguished: 1) elements generally below detection
limit in both phases, 2) elements with significantly more analyses above
detection limit in the FI-rich areas, and 3) elements generally detectable
in both phases. In sample GF-185, group 1 elements are Co, Ni, Ag, Ce,
W, Au and Bi (Fig. 8). Among group 2 elements, average concentration
values of B, V, Rb, Sr, Cs and Ba are at least a magnitude higher in FI-
rich areas; other elements of the group (Mg, Ti, Mn, Fe, Cu, Zn and Pb)
are more often detected in these sections but their average concentra-
tions are not significantly higher than those in the quartz spot analyses.
Similarly, in group 3, Li, Na, K and Sb are significantly enriched in the
high fluid:matrix zones (Fig. 8), whereas Ca shows values similar to
those in quartz.
Profiles a03 to a05 in sample GF-185 transect euhedral quartz
having a simple primary zonation that is composed of FI-inundated
inner growth zones (zones 1 and 2) and a FI-poor mantle (zone 3) with
occasional and isolated secondary FIPs (Fig. 5). The aim of these three

5
G. Tuba, et al. Chemical Geology 529 (2019) 119326

Fig. 4. Visual comparison of an unprocessed LA-ICP-MS acquisition signal and the trace of the respective profile (a07 of sample GF-185) in a zoned euhedral quartz
grain variably inundated with FIs. (Spot size: 50 μm by 50 μm; scanning speed: 3 μm/s.) Note that the fluid-indicative elements are defined by signals which closely
follow the variance in the quartz:FI ratio, namely K, Sr, Rb, Ba, Na, Sb, As and Zn in this example. Other elements are either independent of the quartz:FI ratio (Si) or
inversely proportional to it (Li), hence indicating an affinity to the quartz matrix. Note that whereas both the Ca and B signals do follow the variance in FI abundance,
they are not as sensitive indicators of FIs as for example K or Sr because their background concentration in the matrix is relatively high (cf. zones 1a and 1b).

6
G. Tuba, et al. Chemical Geology 529 (2019) 119326

Fig. 5. Laser ablation traces and profiles and time series data for high FI-density quartz growth zones in sample GF-185. (a) Traces of LA profiles a03 to a05 across
euhedral quartz having a simple, 3-fold growth zonation. These profiles were used to assess data reproducibility across zones with the same primary FIA. (b)
Comparison of the LA trace profiles in quartz and their equivalent TSD diagram converted from the acquired LA-ICP-MS signals. Data representative to specific zones
and transitional areas between them were selected by lining up the TSD with the beam trace (a05 not shown), color-coded and plotted on ternary diagrams. (c)
Ternary diagrams with the TSD for the different zones in the LA profiles color-coded and additional data for quartz spot analysis (a22 to a24) included for
comparison. Data from specific zones (zones 1 and 2, secondary FIs and quartz) cluster in contrasting compositional fields whereas transitional areas (i.e., analyses
across zone boundaries) define three trends among endmembers. The four main clusters defined in the Na-K-Ca ternary are also seen in the two selected trace-element
ternaries provided, Li-Sr-Ba and As-Rb-V. Given that the element ratios of the specific zones are very similar in all three profiles, good reproducibility of the data in
the different zones is indicated.

profiles was to check the viability and reproducibility of the acquired
data along different profiles in the same crystal. The Na-K-Ca ternary
(Fig. 5c) shows that primary FIs of all three profiles plot into two,
slightly overlapping data clouds in the K-rich part of the ternary, each
representing a fluid-dominated growth zone (zones 1 and 2), whereas
inclusion-free quartz (spot analyses a22 to a24) cluster in the Ca apex.
In contrast, where the beam intersected the transitional areas between
zones of different FI abundance (i.e., mixture of zones 2 and 3), the
resulting data plot along trends. Trend 1 is defined between zones 1 and
2 and the FI-free quartz composition at the Ca-dominated apex, whereas
trends 2 and 3 originate in the quartz and primary (zones 1 and 2)
fields, respectively, and converge towards a mixed Na-K-Ca composi-
tion. Based on the presence of secondary FIPs in the quartz-dominated
zone 3, we interpret the Na-K-Ca domain where trends 2 and 3 termi-
nate as the compositional field for secondary FIs in the sample. It is
important to emphasize, however, that secondary FIAs were not di-
rectly analyzed in this sample, and so this is an indirect method for
determining a hypothetical chemistry for this group of inclusions.
Trace-element data for profiles a03, a04 and a05 are plotted in re-
presentative ternary diagrams (Li-Sr-Ba and As-Rb-V, Fig. 5c). As with
the major element plot for Na-Ca-K, groups are defined which equate
the distinctly different chemical signatures for the primary FIs in zones
1 and 2 and the secondary FI population in zone 3. The FIs in zone 1
appear to be relatively more enriched in Ba, Sr, Rb and V than zone 2,
whereas both primary zones have markedly different FI compositions
than the inferred secondary FIAs. Furthermore, it is noted that the
chemistry for the host quartz is depleted in Sr, Ba, Rb and V and falls at
the Li and As apices of the ternaries and thus very different than the
fields for the FIs.
Profiles for another euhedral quartz grain from the same sample
with multiple growth zones (Fig. 6) were used to check for internal
consistency of data obtained with different instrumental settings, and to
confirm primary fluid composition by analyzing multiple grains of the
same sample. Ten consecutive growth zones were analyzed along two
profiles, a07 and a08 (Fig. 6a, b), with contrasting beam diameters and
scanning speeds of 50 × 50 μm and 3 μm/s versus 26 × 26 μm and
13 μm/s, respectively (Table 1). Data were plotted in the same ternary
diagrams as above with the fields, as established for primary and sec-
ondary FIs as well as quartz, included (Fig. 6c). Note that due to the
overlap of the major element data (Na-K-Ca) for zones 2 and 3 with 4
and 5, they are plotted in separate ternaries.
Zone 1 in profiles a07 and a08 represents FI-poor quartz with oc-
casional secondary FIPs and with additional low numbers of primary FIs
in a08 (Fig. 6a). Furthermore, subzone 1a has lower fluid:matrix ratios
than subzone 1b. Analyses of subzones 1a and 1b overlap in both
profiles and in a07 they define a trend between quartz and the pre-
viously defined secondary FI field (Fig. 6b), whereas the trend in a08 is
slightly more towards the K apex. This slight difference between the
two profiles may reflect the higher amounts of FIs encountered in
subzone 1b during the laser traverse. Data for zones 2 and 3 overlap and
fall along the Na-K tie with low Ca, and are somewhat similar to the
signature for the primary FIs in profiles a03 to a05 but less K-rich. The
data for the a08 traverse again have slightly higher K:Na ratios than the
a07 data. There is considerable overlap of the FI data for zones 2 and 3

7
G. Tuba, et al. Chemical Geology 529 (2019) 119326

Fig. 6. Laser ablation traces and time series data for high FI-density quartz growth zones in sample GF-185. (a) Traces of LA profiles a07 and a08 across a single
euhedral quartz grain having multiple primary growth zones with variable abundances of FIs and hence fluid:matrix ratios with different instrumental settings. (b)
Ternary diagrams for major- (Na-K-Ca) and minor- to trace-element (Li-Sr-Ba and As-Rb-V) compositional data from profiles a07 and a08. The data groups were
selected and plotted as for Fig. 5 with the compositional fields established in Fig. 5c overlain here on the same ternary diagrams to show similarities in element ratios.
Unlabeled compositional fields represent primary FIA in profiles a03 to a05. Note that whereas data from zones 1a and 1b plot along trends between quartz (qtz) and
the field for secondary FIs (sec), data for primary FIA (zones 2 to 10) overlap with the primary fields from Fig. 5c with the exception of two growth zones; see Section
5.1 for further discussion. Data of specific zones are generally similar regardless of the beam settings.

with that of zone 4 and 5 and, in addition, collectively the entire data
for zones 2–7 are noted to define a broad cluster with a change to
higher K:Na ratios for zones 6–7. In contrast to zones 6–7, the data for
zones 8 and 9 show a dramatic change in fluid chemistry with a shift to
Na-rich compositions. The final zone analyzed, zone 10, which was only
measured in profile a08, overlaps best with the FI data for zones 6–7.
The compositional data for FIs from the second grain are in good
agreement with not only the major element chemistry (i.e., Na-K-Ca) for
profiles a03 to a05 for the first grain, but also for the trace elements as
seen in the Li-Sr-Ba and As-Rb-V ternary plots (Fig. 6b). The Li-Sr-Ba
data for all zones 1–10 overlap well with the field for zone 2 in profiles
a03-05, whereas for As-Rb-V the data for zones 6 and 7 define a mixing
trend between the two major clusters for primary fluid composition
measured in profiles a03–05, and data for the other zones mainly fall in
the field for zone 2 FIs in a03-05, but with some being skewed towards
the area for secondary FIAs. The similarity of profiles a07 and a08 and
the good agreement with compositional data from the previous analyses
(a03 to a05) suggest that the contrasting instrumental settings (i.e.,
beam diameter and scanning speed) do not influence data reproduci-
bility.
The third quartz grain analyzed from sample GF-185 (Fig. 7) was
used to further test data validation and its consistency. In this euhedral
grain, a total of 12 growth zones with varying abundances of primary
FIs are defined and were analyzed along profiles a18 and a21 (Fig. 7a,
b). The data set generated in the two profiles was found to be very
similar to those from the previous runs, as shown using the same
ternary diagrams (Fig. 7c). Zones with low fluid:matrix ratio (zones 1a,
b and 12a, b) plot along compositional trends between the quartz host
and the field for primary as well as secondary fields (identified pre-
viously). Zones 2–8 cluster tightly and overlap with the previously
defined fields for primary FIs having high K:Na ratio, whereas zones
9–11 plot along a trend between the Na apex and the primary fields,
similarly to zones 8–10 in profiles a07 and a08. Of particular note is the
difference for the analyses in zones 9 and 10 for profiles a18 versus a21.
For profile a18 the data are more Na-rich whereas for a21 the data are
coincident with the field for high K:Na primary FIs. For the trace ele-
ment ternary plots Li-Sr-Ba and As-Rb-V (Fig. 7c), the data plot in fields
that coincide with the other profiles.
5.2. Low fluid:matrix ratio profiles
Five line profiles were analyzed in sample 144Gap in areas having
relatively low fluid:matrix ratios. In profiles a26, a29, a34 and a36,
single FIAs aligned along FIPs were ablated (Fig. 9a), whereas profile
a38 cuts across several FIAs having different types of FIs (Fig. 9b). The
FIAs selected for analyses represent a spectrum of fluid compositions: 1)
aqueous (a26 and a38); 2) aqueous-carbonic with different H2O:CO2
ratios (a36 and a38); 3) carbonic (a38); and 4) two FIAs containing a
heterogeneous population of aqueous-carbonic FIs due to post-entrap-
ment modification (a29, a34 and a38). The line profiles were supple-
mented by 5 spot analyses of FI-free quartz to establish the matrix
background (a27, a28, a35, a37, a39; Fig. 9a, Table 1).
As expected, the influence of FIs in the 144Gap profiles is much less
significant than in sample GF-185 with the high fluid:matrix ratio.
Instead of clustering as seen in the primary FIAs of GF-185, the profile
data points of the 144Gap sample plot along trends in Na-K-Ca ternaries

8
G. Tuba, et al. Chemical Geology 529 (2019) 119326

Fig. 7. Laser ablation traces and profiles and time series data for high FI-density quartz growth zones in sample GF-185. (a) Traces of LA profiles a18 and a21 across a
single euhedral quartz grain having multiple primary growth zones with variable abundances of FIs and hence fluid:matrix ratios. (b) Comparison of the LA trace
profiles in quartz and their equivalent TSD diagram converted from the acquired LA-ICP-MS signals. The different data groups are selected and plotted as above. (c)
Ternary diagrams for major- (Na-K-Ca) and minor- to trace-element (Li-Sr-Ba and As-Rb-V) compositional data from profiles a07 and a08. The data groups were
selected and potted as for Fig. 5 with the compositional fields established in Figs. 5c and Fig. 6b overlain here on the same ternary diagrams to show similarities in
element ratios (fields representing primary compositions are not labelled). Note that the element ratios and clustering of data are identical to the other profiles.

(Fig. 9c). Data clouds for the different aqueous-carbonic and carbonic
FIAs (profiles a29, a34, a36 and a38) reveal very little compositional
difference and define trends along the Na-Ca tie between the Ca apex,
which represents the host quartz composition, and the Na-rich domain.
The profile for the aqueous FIA in traverse a26 is somewhat different in
that the trend terminates in a more K-rich field compared to all the
other FIAs.
Because of the low fluid:matrix ratio, establishing the fluid-in-
dicative elements in these profiles is somewhat problematic for two
reasons: 1) many of the analytes remain close or below detection limit
probably due to the high proportion of quartz in the mixed signals, and
2) average values are not a good approximation for fluid composition as
the profile data do not form well-defined clusters and the fluid:matrix
ratio is not constant from data point to data point. Although elements in

9
G. Tuba, et al. Chemical Geology 529 (2019) 119326

Fig. 8. Comparison of average element concentrations in FI-rich growth zones (primary FIA; n = 2384) and FI-poor quartz spot analyses (qtz; n = 151) in sample GF-
185. Note that the concentration data are semi-quantitative and emphasis should be given to the relative difference between FI zones and quartz matrix rather than to
absolute ppm values. Analyses above detection limit plotted. (a) Group 1 elements are detected in less than 50% of the analyses in both FI-rich growth zones and the
quartz matrix. Group 2 elements are variably detected in the quartz matrix but are above detection limit in more than 80% of the FI-rich analyses where they are
either (b) significantly or (c) moderately enriched compared to quartz. Group 3 elements are detected in both phases with a frequency of over 90% and are either (d)
enriched in primary FIA or (e) show generally the same levels in both phases.

the a26 profile were more frequently above detection limit than in the
rest of the FIP and quartz analyses, Ti, V, Mn, Fe, Co, Ni, Cu, Ag, Ce, W,
Au and Bi analyses commonly returned values below detection limit in
all three environments (Fig. 10a). Among the elements more frequently
detected in the fluid-bearing profiles, a26 shows at least two orders of
magnitude increase in average Na, K, Sr and Pb as compared to the
quartz analysis (Fig. 10b). This is a significant contrast in composition
even though the average values in the fluid-bearing profiles are strongly
influenced by the low fluid:matrix ratio, and therefore these are the
elements best indicating the presence of the fluid in this profile. Ad-
ditionally, at least an order of magnitude increase is showing in average
Li, B, Zn, Rb, and Cs as well as a moderate increase in Ca (Fig. 10c).
Fluid-bearing profiles a29, a34, a36 and a38 showed at least an order of
magnitude enrichment in B, Na, K and As compared to quartz analyses
and a moderate Ca-increase (Fig. 10b, c). The average concentrations of
other detected elements are generally constant among the fluid-bearing
profiles and quartz analyses (Fig. 10d).
In the density-contoured ternaries of the a26 profile (Fig. 9d), the
major-element composition appears to converge toward the field for
secondary FIs established in sample GF-185, and the data set largely
overlaps with the secondary FI field in the Li-Sr-Ba ternary too. The As-
Rb-V ratios of a26 define a trend between the slightly Rb enriched field
to the As apex (Fig. 9d), representative of the GF-185 secondary FIs and
the FI-free quartz composition, respectively.
6. Discussion
6.1. Viability and reproducibility of bulk LA data for contrasting
fluid:matrix ratios
Trial runs to test for acquisition of fluid-characteristic elements
were successful in samples with both high (GF-185) and significantly
lower (144Gap) fluid:matrix ratios, but with varying quality of results.
In sample GF-185, the signatures acquired from FI-inundated growth

10
G. Tuba, et al.
zones proved to be well clustered and generally identical - (1) within
profiles, (2) among profiles in the same grain, and (3) among texturally
identical FIAs contained in different quartz grains – which indicates
good internal consistency of data. Scanning speed and beam diameter
do not seem to have a significant effect on the analysis, as suggested by
the good compositional agreement of data between profiles a07 and
11
Chemical Geology 529 (2019) 119326
(caption on next page)
a08. The fluid-representative chemical signature was strong enough in
these profiles to allow the characterization of the contained FIAs at the
major-, minor- and trace-element levels.
In contrast to results for GF-185, analyses for relatively FI-poor
zones in 144Gap fail to cluster, which is most likely a result of the low
fluid:matrix ratio in the analyzed host. Thus, unlike for the FI-rich
G. Tuba, et al. Chemical Geology 529 (2019) 119326

Fig. 9. Laser ablation traces and time series data of low FI-density secondary FIPs in quartz from sample 144Gap. (a) Traces of LA profiles and sampled FI types. (Line
width and spot sizes not to scale.) Note that the last parts of profiles a26 and a29, oblique to the FIP trace, were analyzed to acquire proxies for FI-poor quartz as a
reference, but as the data were more scattered than for the spot analyses (a27, a28, a35, a37, a39) they were discarded. The LA traces a26, a29, a34 and a36 sample a
single FIP along strike, whereas trace a38 crosses several different FIAs. (aq: aqueous, aq-carb: aqueous-carbonic, het: heterogeneous) (b) Close-up of LA trace a38
showing analyzed FIA (i.e., carb, het, aq-carb) along the beam path. The concentration changes of Na and K in the fitted time series data diagram reflects the
contrasting sections of FI-rich and –poor areas along the profile. The TSD diagram was used to extract FIA-specific data. (c) Ternary Na-K-Ca plots for the different FIA
and FI types acquired from various LA profiles along with spot analyses for quartz. Because of the relatively low fluid:matrix ratios of these LA profiles, the data do
not cluster and instead define trends along the Na-Ca tie between the Ca-dominated quartz matrix and a more Na-rich endmember fluid that likely reflects the actual
composition of the FIs. All the compositional trends are essentially similar, except for the aqueous FIA in profile a26 that shows a distinctly K-rich trend. (d) Density-
contoured ternary diagrams for the aqueous FIA data in profile a26, with overlays for quartz (qtz), secondary FIs (sec) and transitional trend, as defined in Fig. 5c
(sample GF-185). The data for profile a26 plot in and along these fields for both the major- (Na-K-Ca) and minor- to trace-element (Li-Sr-Ba and As-Rb-V) ratios.

growth zones in GF-185 where it is possible to get a high number of abundance of FIs, hence total abundance of FIs ablated and fluid vo-
consecutive readings at relatively constant and high fluid:matrix ratios, lume released. Consequently, minor- and trace-element components of
the fluid:matrix ratio varies from reading to reading depending on the the fluid are either below detection limit or get masked by the trace-
dip angle of the analyzed FIP relative to the sample surface and its element composition of quartz, which is the case for all profiles but a26

Fig. 10. Comparison of average element concentrations in aqueous secondary FIP (sec FIA (a26); n = 688), aqueous-carbonic secondary FIAs (sec FIA (excl. a26);
n = 3929) and FI-poor quartz spot analyses (qtz; n = 437) in sample 144Gap. Note that the concentration data are semi-quantitative and emphasis should be given
to the relative difference between FI zones and quartz matrix rather than to absolute ppm values. Analyses above detection limit plotted. a) Group 1 elements are
detected in less than 50% of the analyses in all types of secondary FIPs and the quartz matrix. b, c) Group 2 elements are variably detected in the quartz matrix but are
above detection limit in more than 90% of the aqueous secondary FIP and 70% of the other secondary FIPs. The aqueous secondary FIP is significantly enriched in Na,
K, Sr and Pb compared to the quartz matrix (b) and moderately enriched in various other group 2 elements (c). d) Group 3 elements are usually above detection limit
and are equally enriched in all three phases.

12
G. Tuba, et al.
in the 144Gap sample.
With this method, it was possible to trace the chemical contrast
between the quartz matrix, primary FIs and several types of secondary
FIAs. The major-element results in GF-185 are in general agreement
with the composition of FIs determined using microthermometry; that
is a contrast between the Na-K primary FIs and Na-K-Ca secondary FIs is
clearly present in the LA data. However, as it was not possible to pre-
determine the absolute Na-K-Ca and trace-element concentrations by in
situ LA-ICP-MS analysis of individual FIs, it cannot be gaged how ac-
curately the compositional fields outlined with the bulk method reflect
actual fluid compositions. Nevertheless, the excellent reproducibility
and robustness of the data for both major (Na, K, Ca) and minor to trace
element levels (e.g., Li, Ba, Sr, As, V, Rb) and the general agreement
with independent chemical analysis suggest that the results are in-
ternally consistent and can, therefore, be used in context with other
types of FI analyses.
The lack of data clustering in the low fluid:matrix ratio sample
(144Gap) makes it somewhat less straightforward to assess fluid com-
position. The example of secondary FIs in GF-185 showed that it is
possible to infer a fluid composition from trends where one endmember
is known. In the 144Gap sample, the mixed signals always come from
the quartz matrix and one specific FIA that is either homogeneous or
composed of FIs modified by post-entrapment deformation.
Modification may result in the change of absolute salinity, but does not
alter the ratio of contained cations (in inclusions without daughter
minerals), therefore the only factor that may cause the Na-K-Ca ratio to
shift is likely the amount of contained quartz (with high Ca:Na) versus
fluid (lower Ca:Na). Logically it can be assumed, therefore, that the
compositional field closest to representing the fluid itself lies at the Na-
proximal extremity of the acquired trends. Naturally, this approxima-
tion only allows a very rough estimate, whereby the a26 profile for
secondary FIA in 144Gap would have a Na-rich Na-K-Ca composition
and all the others were Na-rich Na-Ca fluids. Even though these esti-
mates are very approximate, the inferred composition of the aqueous-
carbonic FIAs are in general agreement with LA-ICP-MS data for in-
dividual FIs from petrographically similar FIAs from samples in this
deposit (Fig. 11a).
The inferred composition of the aqueous FIA in profile a26 is very
similar to the secondary aqueous fluid composition analyzed in sample
GF-185 (Fig. 9d) in terms of both major- and minor- to trace-element
contents. Although the two deposits are geologically unrelated, both
contain secondary, post-mineralization aqueous fluids that likely
Fig. 11. Comparison of selected FI compositions in sample 144Gap acquired using the bulk LA method from this study versus LA-ICP-MS data for individual FI and
evaporate mound analysis (EMA) using the SEM-EDS. (a) Ternary Na-K-Ca plot for aqueous-carbonic FIs showing data acquired from LA profiles in this study versus
LA-ICP-MS data for individual FIs (Kontak and Tuba, 2018). The two datasets are seen to overlap along the Na-Ca limb of the ternary. (b) Ternary Na-K-Ca plot for
secondary aqueous FIAs in different Abitibi orogenic gold deposits (Kontak and Tuba, 2018) determined by EMA and single-inclusion LA-ICP-MS analysis versus
secondary aqueous FIAs analyzed by the LA bulk method of this study. Highlighted areas show the secondary aqueous field established in GF-185 (sec?) and the 0.4
points/cell density boundary of profile a26.
13
Chemical Geology 529 (2019) 119326
represent regional basinal brines reported for many orogenic deposits in
the Canadian Shield (e.g., Olivo et al., 2006; Neumayr et al., 2007;
Rezeau et al., 2017; Kontak and Tuba, 2018). Laser ablation data of
individual FIs and evaporate mound analysis carried out on this late
fluid in other Abitibi deposits (Kontak and Tuba, 2018) are in good
agreement with the estimated compositions based on the bulk LA
method (Fig. 11b).
6.2. Comparison of the LA bulk analysis method with conventional fluid
inclusion studies
This study provides insight into a new analytical protocol to acquire
chemical data for FIs that, due to their size and population density,
preclude being analyzed with more conventional methods. In addition,
the results validate the procedure applied to representative samples
from relevant orogenic gold deposit settings. Some of the important
implications of the LA bulk analysis method in the context of FI studies
applied to ore deposit settings are provided below.
1 The LA bulk method can effectively distinguish among fluids with
different chemical properties even in samples with relatively small
FIs. As we have noted above, such material is common in a variety of
high fluid flux settings and/or where rapid growth textures occur
(Fig. 1). The chemistry acquired from such analyses can thus be used
to both detect and discriminate the chemical evolution of an ore
system where conventional microthermometry and evaporate
mound analysis on such FI populations would fail. Thus, the method
provides insight unattainable otherwise.
2 Sample preparation and analysis are fast and easy and the method
does not require an internal standard established by often laborious
microthermometry.
3 This method can provide invaluable insight into fluid evolution in
growth-zoned samples, such as GF-185, due to its spatial resolution.
Also relevant is the visual trace provided by the method for future
reference if needed. The applicability of the method to such samples
has been well illustrated using several profiles (e.g., a03-05, a07-08,
a18, a21; Figs. 5–7), which clearly show that not only do the in-
dividual growth zones define well-constrained chemical groups, but
also apparent are gradual to abrupt changes in fluid composition
during crystal growth in regards to both the major- and trace-ele-
ment chemistry. For this study, the latter is reflected by the recur-
ring relative enrichment or depletion of fluid chemistry in multi-
G. Tuba, et al.
Fig. 12. Reconstruction of the inferred evolution of the fluid composition for major- and trace elements during quartz crystal growth in sample GF-185 based on the
bulk LA analysis method of this study. The model path, which summarizes all profile measurements, suggests the initial fluid (1) became slightly more K, Ba, Sr, and V
enriched (2) before a sudden relative increase in Na, Li and As occurred (3). Fluctuation of these element ratios resulted in another increase in K, Ba, Sr and As (4) and
finally a less pronounced shift toward Na, Li, Rb, and V (5) and lastly As (6). The composition of the inferred secondary fluid (S) is in contrast with all of these
chemical fluctuations.
element chemical space using selected ternary plots – Na-K-Ca, Li-
Sr-Ba, As-Rb-V (Fig. 12). Such a fluid-chemical path would not be
possible to reconstruct using any of the conventional methods em-
ployed in FI studies, either because of the lack of adequate chemical
and/or spatial resolution (e.g., microthermometry, evaporate mound
analysis) or because the inundated growth zones are not suitable for
conventional in situ LA microanalysis. This has important implica-
tions for ore deposit studies, as changes in fluid chemistry is both
expected and observed in many ore deposit types and often equates
with onset of mineralization (e.g., Audétat et al., 2000; Kontak and
Clark, 2002; Fall and Bodnar, 2018; Rottier et al., 2018).
6.3. External data integrity in comparison with existing LA-ICP-MS data
To further assess data validity, the profiles representative of primary
fluid compositions in the Grey Fox orogenic gold deposit (GF-185) are
compared to LA-ICP-MS data acquired for individual FIs for orogenic
gold, intrusion-related gold (IRG) and Ag-Sb veins, and porphyry ore
deposit settings in Fig. 13. The data are plotted in three ternaries - Rb-
As-Ba, Rb-B-Sr and Cu-Sb-Zn - to accommodate available literature data
and be discriminative in regards to the different deposit types. We note
that this is not intended to be an in-depth assessment of such plots, but
merely an attempt to compare and contrast the newly generated data of
this study with some similar data in the literature. The individual GF-
185 profiles cluster and overlap with the exception of profiles a03 to 05,
which appear to be more enriched in Cu than the other profiles relative
to Sb and Zn (Fig. 13a).
Compared with various barren and variably mineralized orogenic
veins (Fig. 13b), the Grey Fox data is similar to: 1) barren orogenic
quartz veins of the Rhenish Massif, Germany (Marsala et al., 2013) in
the Rb-As-Ba ternary; 2) barren and gold-bearing orogenic veins in the
Rb-B-Sr ternary (Rauchenstein-Martinek et al., 2016; Fusswinkel et al.,
2017); and 3) mineralized orogenic veins from the Neoarchean of
Finland (Fusswinkel et al., 2017) in the Cu-Sb-Zn plot. Also overlapping
with the latter, are data for Ag-Sb vein deposits of the Coeur d’Alene
district, USA, which Hofstra et al. (2013) argue are mixed magmatic-
metamorphic fluids. Of note is that the data for Grey Fox differ for FI
data for the Carlin samples in all the ternary plots. Large et al. (2016)
argue based on the FI data that the deposits studied are of magmatic
origin. Lastly, data for Neoarchean BIF-hosted gold vein systems in
Brazil differ from the Grey Fox data in the Cu-Sb-Zn ternary.
In terms of magmatic-related ore systems, the Grey Fox data are also
compared to FI data for IRG (Ridley, 2008; Schindler et al., 2016) and
porphyry (Ulrich et al., 2002; Williams-Jones and Heinrich, 2005;
Landtwing et al., 2005; Klemm et al., 2007) systems. As is evident from
14
Chemical Geology 529 (2019) 119326
the plots, there is no strong overlap of any of the fluid chemistry, which
strongly suggests a non-magmatic geochemical affinity of these fluids.
This summary and comparison of the data for the Grey Fox sample
analyzed shows that the bulk LA method for analyzing FIs is capable of
producing fluid-chemical data that are both specific to an ore system
and allow comparison with similar data for other hydrothermal ore
settings. In this case, the data presented suggest that for Grey Fox the
fluid chemistry, as constrained by element ratios, is more similar to
data for metamorphic settings.
6.4. Evaluation of the method and future work
The results of the current study, the first of its kind that we are
aware of, show that bulk analysis of FIs using a modified laser ablation
analytical protocol offers promise for determining elemental ratios of FI
populations. Among the advantages of the method are the fast and easy
sample preparation and the excellent visual control on data acquisition.
Relatively low salinity and small FI size do not seem to preclude using
such material such that a robust chemical signal can be obtained if the
FI abundance (i.e., fluid:matrix ratio) in the sample is adequate. It is
apparent from the above that element ratios work well and provide a
basis for fluid discrimination. Importantly, it appears that the ratios are
not influenced by partial ablation (if no daughter mineral is present) or
deformation/modification of fluid inclusions. In addition, fluid salinity
estimates, which can be an issue for some FIAs, are not needed. Where
good quality signals are obtained reflecting high fluid:quartz ratios,
minor- and trace-element ratios can be obtained which are critical for
contrasting fluid types and fluid evolution in an evolving hydrothermal
system.
Beside the positive results, the bulk LA method also has, at present,
some significant limitations in the areas of sample requirements and
methodology, which are addressed in detail in the following sections.
6.4.1. Required FI abundance and size
The minimum FI abundance needed to generate meaningful data is
a crucial question, as illustrated by the 144Gap sample. Low fluid:ma-
trix ratios may become critical for elements whose total mass in the
volume of ablated fluid approaches that of the mass of the same ele-
ment in the ablated host (in this case quartz). Loosely and/or hetero-
geneously distributed FIs in the analyzed FIAs and FIPs oriented at a
high angle to the laser path also result in very variable fluid:matrix ratio
along the profile, which, together with low fluid:matrix ratios, prohibits
the clustering of the data, as seen in the 144Gap sample and the sec-
ondary FIAs intersected in GF-185. To breach a high number of inclu-
sions in any one pulse is also important considering that the timing of
G. Tuba, et al. Chemical Geology 529 (2019) 119326

Fig. 13. Selected trace element data plotted as ratios in ternary diagrams (Rb-As-Ba, Rb-Ba-Sr, Cu-Sb-Zn) which compares data for sample GF-185 acquired with bulk
LA to literature data for various hydrothermal fluid types and ore systems obtained using individual FI analysis by LA-ICP-MS analysis. (a) Data for sample GF-185
showing results from primary growth zones only. (b) Data for mineralized and barren vein samples from orogenic and sediment-hosted hydrothermal environments.
Red field marks the area where 75% of the GF-185 data are contained. Note the GF-185 field is proximal to or overlaps with data for barren and mineralized orogenic
veins in the Rb-As-Ba and Rb-B-Sr ternaries, whereas for the Cu-Sb-Zn ternary there is good agreement with the orogenic gold data. Results for Carlin and BIF-hosted
gold systems plot in different fields. (c) Data for intrusion-related gold (IRG) and porphyry deposits compared to field for GF-185 (red outline). Although partially
overlapping with outlier analyses for other deposit types, the Grey Fox data generally plot distal to the main fields for both IRG and porphyry deposits.
(Data from Ulrich et al., 2002; Williams-Jones and Heinrich, 2005; Landtwing et al., 2005; Klemm et al., 2007; Ridley, 2008; Marsala et al., 2013; Hofstra et al., 2013;
Garofalo et al., 2014; Morales et al., 2016; Schindler et al., 2016; Large et al., 2016; Rauchenstein-Martinek et al., 2016; Fusswinkel et al., 2017)

15
G. Tuba, et al. Chemical Geology 529 (2019) 119326

Fig. 14. Box plot diagram demonstrating the variability of selected absolute element concentrations calculated by subtraction of different quartz matrix analyses.
Calcium, Ti and Fe are highly variable in both samples. Additionally, wide compositional ranges of Li, K and Sr are present in GF-185 (light grey), whereas in 144Gap
(dark grey) B and Ba change quite significantly, suggesting a compositional contrast among quartz grains not only within a given sample but also between the two
quartz veins. (Whiskers indicate minimum and maximum values, bottom and top of boxes are Q1 and Q3, lines and black circles depict median and mean values,
respectively.)

16
G. Tuba, et al.
inclusion burst within the sweep cycle coupled with the possible frac-
tionation of elements due to different wash out times may result in
skewing the laser spectrum (Pettke et al., 2000). Petrographic estima-
tions shows that in the densely populated growth zones of sample GF-
185 the number of FIs breached during a complete sweep cycle is
several tens at minimum, therefore the above issue is likely insignif-
icant in this case. As a contrast, in the loosely packed secondary FIPs of
sample 144Gap this number is very low (< 5 inclusions) and this may
be reflected in the data quality.
Another aspect that may play a role in the contrast of data quality
between the two studied samples is the size of inclusions and thus the
mechanism by which they decrepitate upon ablating. The growth zones
of GF-185 are composed of minute FIs with a very homogeneous size
distribution of typically 1–2 μm. These inclusions were analyzed with a
significantly greater beam size of 50 × 50 μm and thus most of them
likely ablated in their entirety into the plasma. Partial ablation,
splashing and/or bleeding into the chamber (Günther et al., 1998)
probably occurs at the fringe of the beam area in the damage zone, but
these not necessarily affect the analysis significantly as the proportion
of these areas is low compared to the ablated volume and the FIs
contain no daughter minerals that would skew the element ratios if
removed. Partial opening instead of total ablation within the analyzed
volume is much more likely in the 144Gap sample, where the size
distribution in some of the FIAs ranges from 1 μm up to 10 μm.
These aspects demonstrate that the minimum required FI abundance
varies for each case as it logically depends on fluid salinity and chem-
istry (i.e., concentration of elements in the fluid), but the example of
GF-185 shows that about 5–6 vol% uniformly distributed, moderate-
salinity inclusions are adequate to acquire a good quality data set. Small
(< 3 μm) inclusions are likely better candidates for the method than
larger ones.
6.4.2. Homogeneity of the analyzed FIA
Our experiments presented here have been set up such that the
target either contained a single fluid (growth zones in GF-185 and
secondary FIPs in profiles a26, a29, a34 and a36 of 144Gap) or the
different analyzed FIAs were spatially separated (profile a38 crossing
various FIAs in 144Gap), which allows the extraction of FIA-specific
data from the respective TSD section. Although data from sample
144Gap are of lower quality due to the low fluid:matrix ratio, the re-
sults presented here proved to be remarkably consistent and effective in
measuring densely fluid-populated growth zones (GF-185) to the point
where minor- and trace-element variations can be outlined, potentially
suggesting changes in fluid composition during quartz growth. Thus,
with the protocol used here, i.e., analysis of large numbers of FIs and
plotting elemental ratios, extracting meaningful signals from compli-
cated FI populations would be possible if the FIAs are spatially sepa-
rated. Although the euhedral, crustiform quartz of the Grey Fox veins is
somewhat atypical to orogenic gold deposits based on our experience,
such crystal types are abundant in epithermal deposits where this
method could be of potential use. Another application is where mi-
nerals opaque to white light are known to contain abundant FIs, such as
pyrite, wolframite, stibnite, and enargite (e.g., Lüders and Ziemann,
1999; Hagemann and Lüders, 2003; Kouzmanov et al., 2010; Lüders,
2017). By first locating areas of high FI populations using infrared light,
such regions can be analyzed in the manner described here and large
amounts of fluid-chemical data generated, although high elemental
background concentrations will of course be an issue. This method may
be particularly relevant in cases where salinity values are compromised
due to the variability of infrared intensity and mineral chemistry which
is known to affect Tmice and thus inferred fluid chemistry, as discussed
by Lüders (2017).
The lack of spatial separation, i.e., the overlap of several FIAs of
chemically distinct fluids remains a problem, and assessing the
method’s viability in such complex samples, which commonly typify
orogenic quartz vein samples, remains to be investigated. In this case
17
Chemical Geology 529 (2019) 119326
we cannot rely on the spatial resolution of the proposed bulk method
and likely would have to focus on statistical solutions.
6.4.3. Absolute element concentration data
One of the most significant limitations of the method is that it can
offer no absolute concentration data as the number of inclusions ana-
lyzed and, thus, the amount of contained fluid-specific elements vary
from detection to detection. Of course, this problem can be obviated if
sufficient salinity determinations can be obtained to ensure a similar
salinity in the FIA. In such cases, a similar protocol as used in con-
ventional in situ LA-ICP-MS analysis of individual FIs would be em-
ployed.
A logical step towards an attempt to calculate absolute concentra-
tion data with the bulk method would be the subtraction of the quartz
matrix from the acquired signals; however, the heterogeneity of quartz
poses a problem, as the composition of quartz can vary considerably
depending on its setting and even within a single grain (Allan and
Yardley, 2007; Jacamon and Larsen, 2009; Breiter et al., 2013;
Ackerson et al., 2015; Müller et al., 2015; Mao et al., 2017). To assess
the effect of heterogeneous matrix contribution to fluid composition in
the present study, we subtracted the different quartz profiles from the
respective bulk FI analyses, and summarized the results in Fig. 14.
Assuming homogeneous fluid compositions throughout the analyzed
FIAs, all intervals of the raw profile signals representing the targeted
FIA (i.e., intervals with relatively high fluid:matrix ratios) were in-
tegrated to calculate the (averaged) absolute fluid composition by using
the LA-ICP-MS data reduction software SILLS (Guillong et al., 2008). As
an internal standard, the average salinity of 7.7 wt% NaCl equiv. was
used for GF-185 profiles a03-05, a07-08 as well as a18 and a21,
whereas for a26, a29 and a36 in 144Gap we used 16.1 wt% and 4.7 wt
% NaCl equiv. respectively (based on microthermometry data of similar
FIAs in the same samples). For matrix subtraction, homogeneous in-
tervals at least 10 s long were integrated in profiles a23-24 (GF-185) as
well as a27-28, a35, a37 and a39 (144Gap). The selected box plots in
Fig. 14 show that the calculated fluid compositions are highly variable
regarding elements with significant heterogeneity in quartz (e.g., Ca,
Li), and that the 144Gap matrix composition is more homogeneous, and
thus produces narrower compositional ranges, than the Grey Fox
quartz. The implication of these findings is that if, in the future, at-
tempts are being made to quantify element concentrations acquired by
this method, matrix heterogeneity has to be taken into consideration
and analyses designed such that it can be overcome as a difficulty.
Establishing the matrix composition as spatially close as possible to the
analyzed profile would be essential, but given the nature of these
samples (i.e., very highly populated with FIs) in itself will prove to be
problematic. Furthermore, by integrating the entire profile signal into
one averaged data point assuming homogeneous fluid chemistry over
the whole analysis may be misleading, as seen in the case of Grey Fox
profiles a07-08, a18 and a21. This is an area of future development;
however, we see the major application of the method as a tool to dis-
tinguish chemically contrasting fluids and resolve small-scale chemical
fluctuations, and these are entirely possible by using element ratios
without the need of quantification.
6.4.4. Intragrain matrix heterogeneity
As Fig. 14 demonstrates, the average trace element composition of
the quartz matrix may vary significantly among grains of the same
sample. This variation in itself does not affect the mapping of fluid
chemical changes within a single grain when element ratios are used.
Chemical zonation within the host, however, may influence the element
ratios in the mixed fluid-quartz signals, therefore this issue needs to be
addressed.
Cathodoluminescence (CL) imagery reveals an essentially homo-
geneous quartz matrix in sample 144Gap (Fig. 15a), thus the problem of
matrix heterogeneity is negligible in this case. However, strong in-
tragrain zonation is present in GF-185 (Fig. 15b, c). The chemical
G. Tuba, et al. Chemical Geology 529 (2019) 119326

Fig. 15. Zonation characteristics of the quartz host in 144Gap and GF-185. (a) Cathodoluminescence image showing a homogeneous quartz matrix in the analyzed
area of 144Gap. (b) Cathodoluminescence image of the quartz grains hosting profiles a18 and a21 (GF-185). Outlines of growth zones as delineated by FIs are
overlain (yellow dashed line). The fine zonation of quartz as shown by CL does not line up with the boundaries of growth zones indicated by primary FIs. (c)
Cathodoluminescence image of the quartz grains hosting profiles a03 to a05 (GF-185). Outlines of growth zones as delineated by FIs are overlain (yellow dashed
line). The zonation of quartz as shown by CL matches the boundary of growth zones 2 and 3 as indicated by primary FIs. (Halo around LA channels are edge effect on
the CL image.) (d) Time-slice data set of the quartz depth profile a23 in GF-185. Slight zonation of Na occurs with concentrations dropping between about 17–27 s;
other element concentrations are constant. The data set represents ca. 120 μm of material. (e) Time-slice data set of the quartz depth profile a24 in GF-185. Slight
zonation of Na occurs along with a coupled zonation of K and Li. The data set represents ca. 120 μm of material.

nature of this quartz zonation cannot be directly determined because of enrichment between barren and FI-rich quartz and the good reprodu-
the large amount of FIs in the growth zones but inferences can be made cibility primary FIA data in variably zoned matrix), it may be assumed
on the level of contribution of certain elements to the mixed LA signals that chemical zonation of the quartz host does not influence sig-
due to quartz heterogeneity. Considering the fluid-indicative elements nificantly the characteristic (i.e., fluid-indicative) element ratios of the
(Fig. 8), the depth profiles of FI-free quartz spot analyses a23 and a24 FIAs.
show no significant zonation of B, V, Rb, Sr, Ba and As, slight zonation
of Na as well as coupled zonation of Li and K in a24 on an order of
6.4.5. Requirements for future work
magnitude level in concentration (Fig. 15d, e). The depth profiles also
The intention of present study was to evaluate whether useful in situ
reveal that these elements, zoned or not, remain on concentration levels
chemical information could be obtained from fluid inclusion groups
significantly below those measured in FI-rich profiles (cf. Fig. 8). Si-
that otherwise would be deemed unsuitable for microanalysis. Although
milarly, FI-poor and FI-rich segments within other profiles (e.g., zone 3
we see much promise in the technique based on the preliminary results
in a03 to a05, zones 1a, 1b, 12a and 12b in a18 and a21 compared to
presented here, these are only the first steps towards a fully functioning
the rest of the signal) also show this sharp contrast in element con-
and routinely applied method. The next, and most important, step
centrations (Figs. 5b and 7 b). (Note that the depth profiles of a23 and
should focus on quantifying data precision by comparing element ratios
a24 only represent ca. 120-μm segments of quartz and would not be
acquired by the bulk method versus analysis of individual fluid inclu-
sufficient to reveal chemical zonation on a larger scale.)
sions of the same FIA. This should be carried out on natural or synthetic
Comparing the CL zonation pattern to the growth zonation deli-
samples that host FIs in homogeneous, densely populated FIAs that are
neated by FIs in GF-185, it appears that the two do not necessarily
suitable for both individual and bulk LA analysis.
match. The underlying CL zonation in the hosts for profiles a18 and a21
Experiments on FIAs with high-salinity FIs containing daughter
is much finer and more complicated than suggested by the FI growth
minerals should be carried out in order to evaluate the effect of partially
zonation (Fig. 15b), and the CL response of the two grains themselves
ablated heterogeneous inclusions on the calculated element ratios. The
are different along the profiles. As a contrast, in the grain hosting
effect of inclusion size on data quality should also be studied closely.
profiles a03 to a05 the CL zonation shows a similar core-mantle type of
zonation as the FIAs (Fig. 15c). Despite this, the semi-quantitative data
for the primary FIAs measured in the five profiles hosted by three 7. Conclusions
variably zoned quartz grains overlap (Figs. 5c and 7 c), suggesting that
the matrix composition has insignificant effect on the analytical results. Orogenic gold deposits are not well understood from the fluid
Based on these observations (i.e., the significant contrast in element chemistry point of view (e.g., Bodnar et al., 2014; Kontak and Tuba,
2017), partly because in situ LA-ICP-MS analyses of individual FIs are,

18
G. Tuba, et al.
in many cases, limited by the high abundance of variable FI types in
superimposed FIAs that populate vein quartz. In an attempt to over-
come the challenge of fully characterizing the fluid chemistry of FIs in
such settings beyond the conventional salinity estimates, a new bulk
analysis approach using laser ablation traversing of FI-rich areas in
quartz has been outlined and preliminary tests evaluated. These results
show that: (1) a robust chemical signal from ablated FI populations can
be detected at a high spatial resolution; (2) the acquired data are re-
producible with high precision; (3) the estimated compositions equate
to LA-ICP-MS data of individual FIs from the same sample; (4) the
method is capable to distinguishing fluid populations at major- and
minor- to trace-element concentrations; and (5) the results are re-
presentative of the ore system based on the comparison with LA-ICP-MS
data on individual FIs from other studies. As such, the method provides
application to a variety of ore deposit settings where conventional LA-
ICP-MS methodology of analyzing individual FIs is challenging. Results
reveal that the main limiting factor of the method is probably FI
abundance and, thus, the low volume fraction of the aqueous compo-
nent of the FI, such that the fluid chemical signal is masked by that of
the ablated host.
Acknowledgements
This work was supported financially by the Goodman School of
Mines and the Mineral Exploration Research Centre of Laurentian
University as well as the Geological Survey of Canada TGI program
(TGI-5). Thanks in particular to Drs. B. Jago and R. Sherlock for their
support, encouragement and recognition of the value of this work. The
fluid inclusion laboratory used in this project at Laurentian University
was established using NSERC funding granted to Daniel Kontak. Zoltán
Zajacz acknowledges the financial support of NSERC in the form of a
Discovery Grant. The LA-ICP-MS facility used for this research was
constructed with the financial support of a Canada Foundation for
Innovation – Leaders Opportunity Fund grant and an Ontario Research
Fund – Small Infrastructure grant to Zoltán Zajacz. We thank Willard
Desjardin of the Harquail School of Earth Sciences for preparation of
fluid inclusion sections and Primero Gold Mining, now McEwen Mining
Inc., for access and sampling at the Grey Fox deposit site, as well as
Tahoe Resources for access and sampling the 144 Gap zone at Timmins
West mine. The review of the paper by Thomas Ulrich and an anon-
ymous reviewer is gratefully acknowledged.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.chemgeo.2019.
119326.
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