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Journal of Geochemical Exploration 116117 (2012) 1727

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Journal of Geochemical Exploration


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

Composition and evolution of crustal, geothermal and hydrothermal uids


interpreted using quantitative uid inclusion gas analysis
Nigel J.F. Blamey
Department of Earth and Environmental Science, New Mexico Institute of Mining and Technology, Socorro, NM 87801, USA
Department of Geology and Petroleum Geology, University of Aberdeen, Aberdeen, AB24 3UE, UK

a r t i c l e

i n f o

Article history:
Received 28 September 2011
Accepted 5 March 2012
Available online 11 March 2012
Keywords:
Fluid inclusion
Gas
Volatile
Geothermal
Hydrothermal
Ore genesis

a b s t r a c t
Quantitative analysis of uid inclusion volatiles is an underutilized methodology. Fluid inclusion volatiles are
analyzed by the incremental crush fast scan method using mass spectrometry. About 100 mg of sample is
partly and progressively crushed between pauses of 5 and 10 min at room temperature while under
10 8 Torr vacuum and the released gases are analyzed by dual quadrupole mass spectrometers. The gases
routinely reported include H2, He, CH4, H2O, N2, O2, H2S, Ar, CO2, SO2, C2H4, C2H6, C3H6, C3H8, C4H8, C4H10,
and benzene. Besides the incremental crush method, uid inclusion gases may also be analyzed by the
bulk cold crush or thermal decrepitation, Raman spectroscopy and gas chromatography.
In geothermal systems and hydrothermal ore deposits, uid inclusion gas data may be used to discriminate
uid sources (meteoric, magmatic), identify processes (boiling, condensation, mixing), constrain redox, correct uid inclusion isochors, apply gas geothermometry, and provide valuable chemical constraints for uid
rock equilibria modeling. CO2/CH4 versus N2/Ar plots as well as N2ArHe ratios are used to discriminate
calc-alkaline magmatic volatiles which have N2/Ar ratios in the 100s to 1000s from meteoric (where the
N2/Ar ratio is ~ 38) and basinal uids (where Ar/He ratios approach 1). Boiling and condensation have negative and positive slopes respectively on CO2/N2 versus total gas plots. Organic compounds derived by Fischer
Tropsch reactions plot as straight lines on SchulzFlory (log of concentration versus carbon number) plots
whereas boiled volatiles and residual uids create deections. Redox is constrained by CO2CH4H2 ratios
or alkanealkene ratios provided the temperature is known. Gas geothermometry, similar to the approach
applied in geothermal wells, is equally applicable to dissolved uid inclusion gases with the CO2CH4H2
geothermometer potentially useful. Isochors can be corrected using the total partial pressures of all gas species dissolved within homogenized uid inclusions by multiplying the gas concentration and values for Henry's Law constants. Fluidrock equilibria modeling is enhanced by knowing the concentration of gases which
control redox and a(H2S) which is vital for gold and base metal solubility constraints.
The methodology is not limited to geothermal and hydrothermal systems and examples are presented from
several geologic systems such as Libyan Desert glass, metamorphic systems, serpentinites, fault uids, and articial meteorites, thus demonstrating the versatility and exibility of the uid inclusion volatile analysis
technique.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Our understanding of geologic systems where fossil uids were
trapped in the form of uid inclusions has greatly benetted from
the data generated by microthermometry, supported by other techniques. Aqueous inclusions provide valuable information as they
trap the actual uids in micron-scale compartments. For example, it
has become common practice to report uid inclusion data in hydrothermal ore deposits because they provide constraints on PT conditions during mineral growth and ore genesis.

Tel.: + 1 575 835 5634.


E-mail address: nblamey@nmt.edu.
0375-6742/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.gexplo.2012.03.001

Most uid inclusion studies report microthermometry data in the


form of homogenization temperatures, and uid salinities derived by
the measurement of the melting depression of ice. Fluid inclusion gas
compositional data are less commonly reported than microthermometry or LA-ICP data, mainly due to the difculty in analyzing the
gases in concentrations below those which inuence phase changes
during microthermometry. Raman spectroscopy has offered improvements over microthermometry, although measurements are applied
to the inclusion's vapor bubble and one must assume that the measurement includes the dissolved gases. There are two main advantages to using Raman spectroscopy; the potential to undertake
single inclusion analysis, and the non-destructive nature of the method. The alternative is to analyze uid inclusion gases by mass spectrometry (Jones and Kesler, 1992; Kesler et al., 1986; Norman and

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N.J.F. Blamey / Journal of Geochemical Exploration 116117 (2012) 1727

Blamey, 2001; Norman and Sawkins, 1987; Parry and Blamey, 2010)
or gas chromatography (Andrawes et al., 1984; Bray and Spooner,
1992; Bray et al., 1991; Burruss, 1987; de Ronde et al., 2005). Fluid inclusion volatiles are released under vacuum by the act of crushing or
heating, and the volatiles analyzed by a quadrupole mass spectrometer, or in the case of gas chromatography are cryogenically trapped
and speciated by slowly raising the temperature. Both methods are
destructive, but offer increased gas species range, superior detection
limits, little sample preparation, and are unaffected by host mineral
thus allowing opaque minerals to be analyzed.
Fluid inclusion gases gained considerable attention from the uid inclusion community in the early 1990s with most of the focus related to
ore deposit and geothermal exploration. One issue of the Journal of Geochemical Exploration was dedicated to uid inclusion gases, their techniques, and exploration case histories (Bray et al., 1991; Burlinson,
1991; Graney et al., 1991; Landis and Hofstra, 1991; Moon, 1991;
Norman et al., 1991; Shepherd et al., 1991; Takenouchi, 1991; Walder
et al., 1991; Wilkins and Jenatton, 1991). However, it became apparent
that bulk analytical methods could not avoid potential contamination
from multiple uid inclusion populations. Until such time as improvements to uid inclusion gas analysis would allow either single inclusion
analysis or at least single crystal or mineral-separate analysis by mass
spectrometry, the advantages of bulk methods remain: (1) analysis of
species that are undetectable by microthermometry and Raman spectroscopy, (2) analysis of opaque minerals, and (3) far superior detection
limits. More recently there has been interest in the petroleum industry
due to uid inclusion stratigraphy mapping with application to geothermal stratigraphy logging by Dilley et al. (2004) and Dilley (2009). Geothermal stratigraphy logging remains a rapid qualitative tool that
provided qualitative data to evaluate potential zones of interest in exploration wells from drill cuttings.
It is not my aim to discuss the methods in detail for conducting
quantitative uid inclusion gas analysis by mass spectrometry as
this is already described in Jones and Kesler (1992), Norman and
Blamey (2001), Norman and Sawkins (1987), and Parry and Blamey
(2010). The objective is to present a range of applications based on
the interpretation of uid inclusion gas data, supported by examples
generated at the New Mexico Institute of Mining and Technology
(NMT) by mass spectrometry. Limited data from gas chromatography
and Raman spectroscopy are available in the literature; these
methods lack the species range of our mass spectrometer system
but where gaseous species are common to the presented diagrams,
the gas interpretation is equally applicable. Numerous papers report
uid inclusion gas data, but interpretation is rare, and the potential
of such data remains to be fully realized.

KOH to remove surface organics, rinsed several times with deionized


water and are then dried below 100 C for 24 h. Nitric acid is also an
effective cleaner for quartz although one must verify in advance that
whichever cleaner is used does not react in any way with the sample
or leave any residue. The match head sized sample is crushed incrementally under a vacuum of ~ 10 8 Torr, producing 6 to 10 successive
bursts. The act of incremental crushing may open a single inclusion or
multiple uid inclusions, but there is no way to control this during the
current procedure. Large vapor-rich inclusions often yield too much
gas which causes the mass spectrometer lament to shut off as a safety precaution. The data acquisition is performed by means of two
Pfeiffer Prisma quadrupole mass spectrometers operating in fastscan, peak-hopping mode. Routinely the system analyses for the following gaseous species including H2, He, CH4, H2O, N2, O2, H2S, Ar,
CO2, C2H4, C2H6, SO2, C3H6, C3H8, C4H8, C4H10, and benzene. The organics may be reported individually or combined as CnHm in mol%.
The instrument is calibrated using commercial gas mixtures, capillary
tubes lled with gas mixtures, and three in-house uid inclusion gas
standards as described by Norman and Blamey (2001). The amount of
each species is calculated by proprietary software to provide a quantitative analysis. H2 can be reliably detected above about 50 ppm
whereas by applying the formulae of Blamey et al. (2012) the 3
sigma detection limit for most inorganic species is about 0.2 ppm
for aqueous uid inclusions.
Evaluating precision and accuracy are always of prime concern in
analytical data with potential errors being sourced by both instrument and sample heterogeneity. Precision and accuracy vary between
species. Seven capillary tubes with 1 mbar encapsulated atmosphere
(Table 1) were analyzed and yielded N2/Ar ratios of 83.4 with a standard deviation of 0.4 in comparison to an atmospheric N2/Ar ratio of
83.6. This translates into 0.5% accuracy for articial inclusions made
under laboratory conditions. Estimating precision is difcult using
natural inclusions owing to an inherent natural variability between
inclusions even in the same population, a problem that does not affect
capillary tubes manufactured in the laboratory. Precision using natural inclusions for the major gas species measured CO2, CH4, N2, and Ar
is ~ 5%, and for minor species is ~10%.
It is important in natural inclusion standards to evaluate if only
one uid inclusion population exists in a sample but it is difcult to
prove gas homogeneity or heterogeneity between inclusions from a
single population. In Fig. 2 the incremental crush analyses from

2. Samples
Unlike Raman spectroscopy where it is critical for the host mineral
to be transparent to the laser, using the mass spectrometry and gas
chromatography methods it is inconsequential whether the mineral
is transparent or opaque. Minerals such as quartz, uorite, calcite, anhydrite, pyrite and halite are routinely analyzed, and several examples are given below. It is routine practice at NMT to analyze
mineral separates or individual crystals as only 100150 mg of material is adequate, sometimes as little as 25 mg. This is an improvement
on other systems that commonly require 510 g of sample. Larger
samples increase the risk of including multiple uid inclusion
populations.
3. Methodology
Fluid inclusion volatile analysis is done in vacuum using the CFS
(crush-fast scan) method described in Norman and Blamey, 2001;
Norman and Moore, 1997; Norman et al. (2002a); and Parry and
Blamey (2010) (see Fig. 1). Samples are rst cleaned with NaOH or

Fig. 1. Simplied schematic of the quadrupole mass spectrometer system showing the
major components. The four crushers house the samples for crushing and during incremental crushing, the liberated gases pass a pressure gauge (P) and the inlet for standard gases (SG) prior to being detected by the two quadrupole mass spectrometers
(QMS). The gases are nally evacuated by a high vacuum (HV) system.

N.J.F. Blamey / Journal of Geochemical Exploration 116117 (2012) 1727

Nant Helen quartz compared to the Raman spectroscopy and microthermometry values were reported by Beeskow et al. (2005) as a potential uid inclusion gas standard. Minor differences between the
methods may be attributed to the fact that Raman data is measured
on the bubble whereas mass spectrometry data includes gases from
the vapor bubble plus gases dissolved in the uid. For comparison, a
quartz vein sample from Mace Head in Ireland (reported by
Gallagher et al., 1992) that hosts multiple uid inclusion populations
is plotted against the NMT in-house natural standard NB-84 which
hosts one uid inclusion population (Fig. 3). The single sample hosting multiple uid inclusion populations has a large spread of data
points which contrasts with the tight cluster for the sample that
hosts one population (Fig. 3).
Andrawes et al. (1984) and Graney and Kesler (1995) reported
that CH4 is generated by crushing under high vacuum, thus invalidating analyses. Our analyses of standard NB-84 by both the incremental
crush in dynamic mode and thermal decrepitation methods provided
the same CO2/CH4 ratio, which also matches the melting point depression of solid CO2 by the microthermometric method. If methane
is being generated by the act of crushing in the NMT mass spectrometer system then the amount of methane is so low as to be insignicant. Actuating the crushers on a piece of blank quartz generated a
very weak methane blip that was 1.52 orders of magnitude lower
than the methane peak generated during normal sample crushing.
The mass spectra for all other gas species remained at background
during crushing of the quartz blank indicating that gases released
are not sourced from the crushers or hardware. The generation of
methane by the act of crushing is therefore considered to be insignificant with the design of this mass spectrometer system.
Another common question requiring explanation is whether an
analysis by mass spectrometry represents the uid inclusion volatiles
or are there other contamination sources from within the sample?
Minerals that lack water in their structure, such as quartz or uorite,
are unlikely to contribute additional water to a cold incremental
crush analysis in dynamic mode although Norman (pers. comm.,
1996) did suggest that the thermal decrepitation method might liberate minor water trapped within the quartz lattice. Landis et al. (2005)
did prove that non-inclusion water was produced by thermal decrepitation. In addition, personal unpublished data shows that some minerals with water in their structure (such as jarosite) have a water

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Fig. 3. Plot of CO2/CH4 versus N2/Ar comparing NB-84 (circles) and Mace Head
(squares). Sample NB-84 has one uid inclusion population whereas the Mace Head
sample (described in Gallagher et al., 1992) is host to multiple uid inclusion populations. This demonstrates the precision for a natural uid inclusion standard as well as
the variability that can occur with a sample host to multiple populations.

vapor pressure in the vacuum system that is one to two orders of


magnitude above 10 8 Torr, thus limiting their analysis. The jarosite
problem is exacerbated with progressive incremental crushing as
new surfaces are created and add to the water vapor. However,
when using the incremental crush method, minerals such as quartz,
uorite, calcite, pyrite and many others are suitable for analysis as additional volatile contributions are unlikely and it may be assumed
that the volatiles analyzed represent inclusion volatiles.
3.1. Comparison between uid inclusion gas analysis methods
Fluid inclusion gas data presented in the literature generally is
measured by one of four methods, namely mass spectrometry, noble
gas isotope analysis (by mass spectrometry), gas chromatography
and Raman spectroscopy. Raman spectroscopy is the only nondestructive method and is concisely summarized in Goldstein and
Reynolds (1994). It requires measuring scattered laser light reected
by molecular vibrations which cause wavelength shifting. Sample
preparation is critical, requiring polished wafers. The bubble-hosted
gases (e.g. CH4, CO2, H2S, N2, H2, O2) are most commonly quantied
in addition to detection of polynuclear species in the aqueous phase
(e.g. SO42 , CO32 , NO3). A severe limitation of Raman spectroscopy
is the detection limits, in addition to a limited gas specie range and
lack of noble gas detection. Nevertheless, it is a truly singleinclusion non-destructive analytical method that offers great merit.
In our incremental crush fast-scan methodology by mass spectrometry, the sample is exposed to the mass spectrometers at all
times and during the act of crushing, all the gases simultaneously permeate the main vacuum chamber. Analysis is dynamic and a turbo
pump removes gases from the main chamber within 2 s. For this reason, quantitative analysis of isotopes is too problematic to be practical
by the incremental crush fast scan method although it is achievable
by the bulk crush or thermal decrepitation followed by cryogenic separation (Landis and Hofstra, 1991; Norman and Sawkins, 1987). Two

Table 1
Lower atmosphere water-free gas composition of selected gases in mole percent
(Mason and Moore, 1982).

Fig. 2. Comparison between microthermometry data and Raman data reported by


Beeskow et al. (2005), and our analyses done by incremental crush and analyzed by
mass spectrometry (80.3 to 83.0 mol% plotted as a box). Our data is in agreement
with the Raman data whereas the microthermometry data appears to be relatively
CO2 depleted (see text for explanation). Analyses are normalized to CO2 + CH4.

N2
O2
Ar
CO2
Ne
He

78.084
20.946
0.934
0.035
0.0018
0.0005

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N.J.F. Blamey / Journal of Geochemical Exploration 116117 (2012) 1727

salinity and homogenization temperatures may be used during microthermometry to correlate or discriminate populations. Similarly, both
Raman spectroscopy and gas analysis by either mass spectrometry
and/or gas chromatography are able to discern uid inclusion gas
chemistry, correlate or discriminate uid inclusion populations, or
show progressive chemistry changes in a paragenetic sequence. This
serves as a rst-pass screening, for example where different minerals
yield distinct salinities it would be desirable to separate them out for
detailed compositional analysis.

limitations of the thermal decrepitation approach are that noninclusion water and gases may be liberated (Landis et al., 2005) as
well as excess hydrogen generated in the vessel at high temperature
(Norman and Sawkins, 1987). Major advantages of the incremental
crush fast-scan method are the species range, detection limit, match
head sample size, and avoidance of non-inclusion uids. Separation
of crystals host to single uid inclusions or petrographically examined
wafers is also practical, thus permitting single uid inclusion gas
analysis.
A variation on the incremental cold-crush fast-scan method is a
non-crush with slow progressive heating and fast scan (Graney and
Kesler, 1995). The sample is slowly heated under vacuum and once
individual inclusions over-pressure above their Th and decrepitate,
their gases are released into the main chamber prior to extraction
by a turbo pump. While there is no control as to when inclusions decrepitate, numerous bursts occur over time and each burst may be
regarded as a single inclusion rupturing, making this method a potential single-inclusion technique. Over a range of temperatures it is possible to have multiple uid inclusion populations decrepitate at
different temperatures (Graney and Kesler, 1995). The limitations of
this method are the possibility that decrepitation of inclusions will
cause a crack to develop that intersects another inclusion, resulting
in multiple inclusions being mixed together. The second limitation
is changing of water absorption characteristics in the main chamber
which will alter the water calibration as temperature increases, thus
requiring correction (Graney and Kesler, 1995).
Noble gas analysis of uid inclusions requires clean up with all
gases except noble gases being scrubbed prior to release of the
noble gases into the main mass spectrometer chamber. In addition,
samples are relatively larger than the mass required for the incremental crush fast-scan methodology by mass spectrometry. Noble
gas isotopes are routinely analyzed in static mode and after analysis,
the main chamber is exposed to a getter that removes the noble
gases. Vacuum quality is generally improved owing to scrubbing of
the non-noble gases prior to release into the main chamber.
Analysis of uid inclusion gases by gas chromatography requires
bulk crushing of about 510 g of sample and the released gases are
cryogenically trapped by liquid nitrogen. The principle of gas separation depends on gas release being controlled by slowly heating the
cryogenic compartment thus releasing gases at different times and
being measured by a mass spectrometer. A detailed description of
the method is presented by Bray and Spooner (1992), Bray et al.
(1991), and Andrawes et al. (1984), with data from black smokers
reported by de Ronde et al. (2005).
Gas chromatography is another bulk method best suited to discriminating organic compounds in petroleum oils (Burruss, 1987).
The relatively low vapor pressure of longer-chain hydrocarbons
makes the gas chromatography method attractive for analyzing alkanes above C6 as well as other petroleum compounds (George et
al., 2007; Jones and McLeod, 2000; Munz, 2001).
It should be noted that the thermal decrepitation or crush with cryogenic separation as described by Norman and Sawkins (1987) may produce slightly different values for uid inclusion gas data. The act of
incremental crushing often does not rupture all inclusions within a
sample. By thermal decrepitation nearly all inclusions rupture but two
problems occur. Firstly excess H2 is generated at high temperature by
the reaction of CH4 and water to produce CO2 and H2 (Norman and
Sawkins, 1987). Secondly, non-inclusion gases or water locked up within the mineral lattice may be liberated (Landis et al., 2005).

It is highly advantageous in metal deposits and geothermal systems to identify the potential uid sources. In ore deposits, uids
sourced from magmatic systems are a valuable source of metals.
However, many geothermal systems are driven by magmaticallyheated meteoric uids without a signicant magmatic component.
Since meteoric uids owe their origin to rainfall, meteoric uids
have similar gas ratios to a glass of water standing in equilibrium
with the atmosphere and this is referred to as air-saturated water
(ASW) (Norman and Musgrave, 1994). Owing to differing partitioning coefcients between atmospheric gases and pure water which
may be calculated using Henry's Law constants, ASW has a N2/Ar
ratio of 38. Giggenbach (1996) collected gas from volcanoes, in
which the N2/Ar ratios were in the 100s to 1000s (Norman et al.,
2002b). This discrepancy between N2/Ar from meteoric versus magmatic uids allowed Norman and Musgrave (1994) to dene a magmatic eld to discriminate meteoric uids from magmatic-related
uids in geothermal systems using a N2ArHe ternary plot. A variation on the N2ArHe ternary plot was the development of the CO2/
CH4 versus N2/Ar diagram (see Blamey and Norman, 2000; Moore et
al., 2001; Norman and Moore, 1999). Meteoric uid is expected to
have N2/Ar ratios that match ASW and plots on the left side of the diagram (Fig. 4a). Norman reports that shallow meteoric uids have
high CO2/CH4 owing to low CH4 concentrations in meteoric uids.
Fluids that have penetrated deep within the crust will have acquired
methane as is demonstrated by basinal uids from the Hansonburg
MVT deposit. Magmatic uids, owing to their high N2/Ar ratios, plot
on the right side of the diagram (Fig. 4a). Gases analyzed from volcanoes have high CO2/CH4 ratios (Giggenbach, 1996) and Norman
(pers. comm., 1999) suggested that uids sourced from deep magmatic systems such as porphyry systems might have a component
of methane that originated from the rocks into which the intrusion
was emplaced, producing a composite uid (see Fig. 4a).
A limitation to the magmaticmeteoric discrimination plot using
CO2/CH4 versus N2/Ar is the occurrence of excess nitrogen in some
geothermal systems reported by Norman and Moore (1999). The
breakdown of protein to yield nitrogen was proposed and a new
eld labeled the organic eld was added to the CO2/CH4 versus
N2/Ar plot (see Fig. 4a). To avoid false discrimination of high
nitrogen-bearing basinal uids plotting in the magmatic eld, another discrimination diagram (Fig. 4b and c) based on N2, Ar and He was
developed (Blamey and Norman, 2002). Knowing that basaltic uids
have N2/Ar ratios that are close to atmospheric, the label for the
magmatic box needing to more accurately describe the gas data,
and since the data was collected from calc-alkaline systems, the
label was accordingly changed (see Fig. 4c). Unpublished data suggests that the box extends to the right and downwards thus in the future the limits of the calc-alkaline box may need to be revised.

4. Controls on applications

4.3. Processes

4.1. Sample discrimination

Fluid inclusions trapped during boiling of geothermal/hydrothermal


uids results in pairs of aqueous-dominated and vapor-dominated inclusions that homogenize at similar temperatures (Roedder, 1984).
Boiling in the system, although not necessarily at the site of trapping,

Most uid inclusion analytical methods can be used to correlate or


discriminate uid inclusion populations. Thus, matching or dissimilar

4.2. Fluid sources

N.J.F. Blamey / Journal of Geochemical Exploration 116117 (2012) 1727

21

Another method to recognize boiling includes the analysis of excess gas during bulk analysis with gas concentrations > 1.5 mol%
(Moore et al., 2001; Norman et al., 2002a,b). The process of boiling results in scrubbing the hot uid of its dissolved gases. Owing to differing partition coefcients between gases, the rst vapor phase to
form is relatively enriched in gases with high partition coefcients
such as methane and nitrogen. Gases with lower partition coefcients
such as H2S become relatively enriched in the residual uid. As a result, ternary plots of CO2CH4H2 or CO2CH4H2S can help to evaluate boiling in open and closed system, y fractions, and changes to gas
compositions (Moore et al., 2000; Moore et al., 2001).

Fig. 4. Plots used to discriminate meteoric versus magmatic uids. Meteoric uids (or
ASW) have a N2/Ar ratio of around 38 whereas the N2/Ar ratio exceeds 100 for magmatic uids (Norman et al., 1994). In panel a, meteoric uids plot on the left side of
the CO2/CH4 versus N2/Ar plot (Moore et al., 2001; Norman and Moore, 1999) whereas
magmatic uids plot on the right. Norman and Moore (1999) noted that amagmatic
uids from the Hansonburg MVT deposit can have elevated N2/Ar ratios and falsely
plot in the magmatic eld and therefore added an organic eld. Using the N2Ar
He plot in panel b (Blamey and Norman, 2002), meteoric uids still plot on the left
side of the diagram whereas Hansonburg MVT brines have higher helium and cannot
only be discriminated from shallow meteoric uids but also from calc-alkaline magmatic gases. In panel c, the squares are represented by stalagmite samples plus supergene calcitehematite from the Thabazimbi Mine where uids are clearly meteoric.
Diamond-shaped symbols represent magmatic gases from several sources that include
volcanoes measured by Giggenbach (1996), the Snowbird pegmatite from Montana,
cuttings from 5300 to 10,000 ft depth in a drillhole from the Coso geothermal eld,
and anorthoclase from Mt Erebus (reported in Blamey and Norman, 2002). The triangular symbols represent Hansonberg uorite, an MVT deposit where mineralization
is clearly amagmatic.

may also be recognized by healed fractures or growth zones containing


only vapor-rich inclusions (J.N. Moore, pers. comm., 2012). However, microthermometry and petrographic examination of a single
sample cannot discriminate between a uid that has not boiled and
a residual uid post boiling. As boiling is commonly associated
with gold mineralization in epithermal systems, being able to identify whether a uid has boiled or not becomes valuable as an exploration indicator.

4.3.1. CO2/N2 versus total gas plot


The effect of boiling in an open system is to reduce the dissolved
gases from the liquid phase in addition to depleting strongly partitioning gases more rapidly than weakly partitioning gases. As bubbles nucleate they are initially enriched in species that have a strong partition
coefcient. The bubble will be enriched in nitrogen preferentially to
CO2 thus relatively depleting the liquid of nitrogen and causing the
CO2/N2 ratio of the liquid to increase while the total amount of gases
decreases. As boiling continues, the liquid becomes further depleted
in gases and nitrogen continues to be scrubbed from the liquid more
rapidly than CO2. As a result, Norman et al. (2002a) suggested that
the CO2/N2 ratio versus the total gases of the boiling liquid will follow
a negative slope as indicated in Fig. 5a. A uid that has boiled will have
a relatively high CO2/N2 ratio and low total gas concentration.
To validate the CO2/N2 ratio versus the total gas diagram, modeling
using PHREEQC (Parkhurst and Appelo, 1999) was conducted based
on initial gas concentrations determined by uid inclusion gas analysis
for sample K9-8-GA, reported by Velador (2010). Initial temperature
conditions selected was 200 C. Each simulation was calculated by applying a 1 ml bubble with no gas and PHREEQC simulated achievement of equilibrium by allowing gases to partition into the gas-free
bubble from the liquid phase. The gases within the bubble were removed from the system and the simulation repeated for 21 simulations
thus incrementally depleting the residual uid of dissolved gases. The
results of this simulation are presented in Fig. 5b. The straight line
with negative slope of ~1 proposed by Norman et al. (2002a) is likely
to be an oversimplication as the curve dened by PHREEQC gas-loss
modeling which only represents the specic conditions modeled.
Changing either the temperature or gas ratios or salinity or gas concentrations are all factors that might change the slope and curve for a boiled
uid. It is therefore suggested that comparing a curve modeled by
PHREEQC to the actual uid would be valuable.
The process of condensation occurs from a vapor that has high gas
concentration with low water vapor. During initiation of condensation,
the initial liquid will dissolve gas thus increasing the total dissolved gas
content. The initial CO2/N2 ratio of the uid will increase because highsolubility CO2 dissolves more readily than low-solubility N2 into the liquid. As the process of condensation advances, more gas becomes dissolved in the water and the CO2/N2 ratio will increase. A limit is
reached once the vapor pressure of the gases equal the ambient pressure
causing the gases to pass through the liquid. The resulting chemistry plotted in gure 5 yields a positive slope whereby the CO2/N2 increases as the
total gas in the liquid increases (see Norman et al., 2002a for details). In
summary, the CO2/N2 versus Total Gas plot presented by Norman et al.
(2002a) demonstrates that a boiling trend has a negative slope.
Norman et al. (2002a) also demonstrate that data produced by the process of condensation plots with a positive slope, and that analyses will
be enriched in gas relative to the original pre-condensation uid.
4.3.2. Organic compounds
The naturally occurring organic compounds present in geothermal
systems are generally in such low concentration that microthermometry
and Raman spectroscopy are ineffective in their analysis. The only
two methods with the sensitivity to analyze the organics are mass

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N.J.F. Blamey / Journal of Geochemical Exploration 116117 (2012) 1727

100

10

CO2/N2

pe

bo

ilin

io
at

slo

en

nd

slo

co

pe

.1

.01
.01

.1

10

100

Volatile content in %
100

Fig. 6. Examples of SchulzFlory plots for geothermal uids (Norman et al., 2001).
Straight-line plots represent hydrothermal uids that have not boiled with organic distribution generated by FischerTropsh reactions. The condensate or boiled vapor is
represented by a curved line where methane is very high as is demonstrated by the
sample from Tiwi 7000'. Residual uids are depleted in methane and plot as a curved
line where propane and butane dominate as is shown for Geysers SB.

CO2/N2

10

.1

.01
.01

.1

10

100

Volatile content in %
Fig. 5. a. The CO2/N2 versus total gas plot has been used to identify boiling and condensation (Norman et al., 2002a). Boiling results in N2 being depleted more rapidly and
therefore the data plots with a negative slope (see Norman et al., 2002a for full description) as is demonstrated by the epithermal data from Mexico. Condensation data plots
with a positive slope. b. Cross-plot of CO2/N2 versus total gas in mole percent used to
discriminate boiling or condensation proposed by Norman et al. (2002a). Superimposed is a PHREEQC modeling for the residual uid based on sample K9-8-GA whose
gas chemistry is reported in Velador (2010). Initial simulation steps match the negative
slope proposed by Norman et al. (2002a) but the slope increases with progressive volatile loss.

spectrometry (Norman and Blamey, 2001; Norman and Sawkins, 1987;


Norman and Musgrave, 1994; Norman et al., 2002a) and gas chromatography (Bray and Spooner, 1992; Bray et al., 1991). FischerTropsh reactions result in the generation of light hydrocarbons and by mass
spectrometry one is able to analyze C1 to C4 alkanes and alkenes. Analyses
for organic compounds generated by FischerTropsh reactions approximate to a straight line on SchulzFlory diagrams whereby methane was
three fold the concentration of ethane, ethane has three times the concentration of propane, and propane three times the concentration of butane. The SchulzFlory plot has carbon number on the x-axis and log of
concentration on the y-axis (see Fig. 6). One can therefore identify nonbiogenic generation of organics in natural systems by straight lines. During boiling, the organic compounds partition into the vapor phase but as
these compounds have differing partition coefcients, the straight line
represented by FischerTropsch reactions becomes distorted (see
Norman et al., 2002a for details). Because methane and butane partition
more favorably into the vapor phase than ethane and propane, the
vapor phase will be relatively more enriched in these two gases causing a concave upward line as seen by the data for Tiwi 7000' in Fig. 6.
Owing to depletion in methane and variations in Henry's Law constants for the other gases, a residual uid from which gases have
boiled can be recognized by a convex upward curve in data from
Geyers SB (see Fig. 6).
4.4. Redox
It is common to report redox in geological systems denoted by
the oxygen fugacity (fO2) or the hydrogen fugacity (fH2). Measuring

oxygen dissolved in hydrothermal and geothermal systems can be


misleading especially since large negative oxygen fugacities imply
that a uid may have less than one molecule of oxygen per liter. Analyzing hydrogen is a more realistic option, although below 300 C
the hydrogen content may be below the detection limit for mass
spectrometry. Analyzing the CH4 and CO2 in a uid offers a practical
means to calculate the hydrogen fugacity from the reaction reported
by Henley et al. (1984):
CH4 2H2 O CO2 4H2 :

A uid inclusion's methane and CO2 can be estimated using microthermometry by measuring the melting depression of CO2 below
56.6 C, provided that the gas level is sufciently high. Raman spectroscopy does allow for the measurement of CH4 and CO2 in the vapor
bubble and the fO2 or fH2 can be estimated from graphs presented by
Giggenbach (1980). To date, mass spectrometry offers the most accurate method to quantify these gases. However, the thermal decrepitation method to liberate inclusions should be avoided because excess
hydrogen is generated (Norman, 1977; Norman and Sawkins, 1987).
The incremental crush method of liberating uid inclusion gases
does not suffer from the generation of excess hydrogen but accurately
measuring hydrogen levels close to the detection limit can result in
errors.
Redox state can be determined using other gases analyzed by
mass spectrometry such as SO2/H2S and organic compounds. In particular alkane/alkene ratios offer a reliable fH2 constraint as suggested
by Norman and Moore (2003).
Organic compounds also provide constraints on redox boundaries
by using equilibria modeling between alkanes and their equivalent
carbon number alkene. This was recognized by Norman and Moore
(2003) who used the following theoretical equilibrium reactions for
oxygen-bearing and oxygen-free environments to constrain the fO2
or fH2:
/

Cn H2n2 1 2 O2 Cn H2n H2 O

Cn H2n 2 Cn H2n H2 :

or

These reactions are temperature dependent and therefore the


equilibrium fO2 or fH2 can be determined at the equilibrium point
where the concentrations of alkane and alkene are equal. Organic
compounds therefore provide redox limits. If the alkane dominates

N.J.F. Blamey / Journal of Geochemical Exploration 116117 (2012) 1727

then the uid is relatively reducing whereas if the alkene dominates


then the uid is relatively oxidizing and a maximum or minimum
fO2 or fH2 can be calculated. The equilibrium redox for propane/propylene and butane/butylene is very close whereas the equilibrium
redox for ethane/ethylene differs by an order of magnitude. It is
therefore possible to have a uid that comprises more ethane than
ethylene yet has more propylene than propane. This case offers limits
on the uid redox below the detection limit for H2 by mass spectrometry (see Fig. 7).
4.5. Geothermometry
Analysis of gases in geothermal wells is one of the approaches
used to evaluate down-hole temperatures (Giggenbach, 1980;
Henley et al., 1984) and is also applicable to uid inclusion studies.
For gas geothermometry to be valid, the gas species must be constrained by a temperature-sensitive reaction whereby the reaction
readily advances in one direction but does not reverse when the temperature decreases. One such example is the reaction given to constrain redox (Eq. (1)). As temperature increases, the CO2/CH4 ratio
increases and hydrogen concentration increases. Once the uid becomes isolated, such as being trapped as a quartz-hosted inclusion,
the gas chemistry is preserved. However, hydrogen at ppm or subppm concentrations in geothermal systems may be problematic,
given the hydrogen detection limit for the mass spectrometer system.
Additional gas geothermometers are known and described in
Henley et al. (1984) as well as Powell (2000). These include the
NH3N2, H2CO, the D'Amore and Panichi (1980) empirical gas
geothermometer, and the CCO2H2 geothermometer proposed by
Nehring and D'Amore (1984). While these geothermometers are routinely used in geothermal exploration where an adequate volume of
gas is extractable from the well, some of the species are difcult to detect in uid inclusions using the cold-crush fast scan method but can
be detected using the bulk cold crush cryogenic separation method.
Norman et al. (1998) and Blamey (2006) discuss a potential H2S
geothermometer that is practical to uid inclusion gases provided
H2S can be accurately measured, the uid has not reacted with sulde
minerals post trapping, and the uid did not boil.
4.6. Isochor correction
Computer programs provided by Brown (1989) and Bakker (2003)
have been valuable to uid inclusionists to calculate isochors and estimate trapping conditions above homogenization temperatures. Simple

Fig. 7. Equilibrium relationships between ethane and ethylene, propane and propylene,
butane and butylene, in terms of hydrogen fugacity and temperature (slightly modied
after Norman and Moore, 2003). Cooling in the absence of boiling promotes the stability of alkanes. During boiling, hydrogen is rapidly lost owing to its high partition coefcient, thus favoring oxidation which promotes alkene formation.

23

isochors were originally based on the pure water or NaClH2O systems


but over time progressively more complex systems have been resolved.
Dissolved gases provide additional internal pressure to the pure-H2O or
NaClH2O isochors.
PTotal PH2O PCH4 PH2 PCO2 P:

where PTotal is the pressure within the inclusion above Th


where PH2O is the pressure exerted by water above Th and is determined by the H2O + salt isochors
where PCH4 is the partial pressure of methane above Th
where PCO2 is the partial pressure of CO2 above Th.
Adding the gaseous component increases the partial pressure
within an inclusion and therefore provides a more accurate estimation of PT conditions within the inclusion. However, accurate determination of the gas concentrations and the values for Henry's Law
constants is essential, particularly gases with high partition coefcients such as methane because these gases signicantly increase partial pressures. Both gas analysis by mass spectrometry and gas
chromatography offer the means to determine the gases with sufcient accuracy to rene the gas-corrected isochors within error.
4.7. Fluidrock equilibria
There are many minerals whose stability is controlled by dissolved
gases within uids especially carbonate, sulde and oxide minerals.
Redox has already been presented as a control for some minerals but
aCO2 and aH2S also control the stability of carbonate and sulde minerals respectively. Key to applying gas data to uidrock equilibria is
quantitative data. Gas ratios within the vapor bubble are insufcient.
It is essential to have control of the entire inclusion's chemistry from
the salt composition through to the gas concentrations. The salts not
only act as ligands for metal complexes but they also change the
values for Henry's Law constants, thus changing the activity and partial pressures of dissolved gas species.
Early use of uid chemistry modeling using uid inclusion gas
analysis addressed calculated uid pH or fO2, fH2 and fS2 (e.g.
Norman and Sawkins, 1987; Norman et al., 1985, 1991; Smith et al.,
1984). Most studies have demonstrated changes in uid gas chemistry but did not progress to calculating pH, redox or sulfur activities
which are valuable ore genesis constraints.
Low H2S concentrations in brines favor the transport of base
metals whereas gold transportation as thiosulde complexes is enhanced in hydrothermal uids with high aH2S (Benning and
Seward, 1996; Seward, 1973; Stefnsson and Seward, 2004). Analyzing the H2S concentration therefore allows geochemists to make predictions about the potential for uids to transport gold as well as to
model the precipitation of metal suldes or calculate the maximum
concentration of Fe, Cu, Zn, Pb that may be dissolved in a hydrothermal uid at any given temperature and salinity. Computer software
such as PHREEQC (Parkhurst and Appelo, 1999) or Geochemist's
Workbench offer the means to predict metal solubility and sulde
stability with the basic analytical input constrained by uid inclusion
gas analysis, microthermometry and LA-ICP-MS data. The microthermometry provides PT constraints as well as uid salinity to which the
ionic ratios can be constrained by LA-ICP-MS data. To this, the gas
data is added thus providing constraints on the uid chemistry for
uidrock reaction modeling.
Modeling gold solubility is feasible using this approach and requires the uid temperature, uid ionic strength, constraints on the
hydrogen fugacity which can be determined from redox, the H2S concentration, and published equilibrium constants (Benning and
Seward, 1996; Stefnsson and Seward, 2004). Using this approach,
Blamey (2000) was able to calculate the maximum gold solubility in
a Carlin-type gold deposit, thus demonstrating that ore uids were
stripped of gold by reactions between ore uids and Fe-bearing

24

N.J.F. Blamey / Journal of Geochemical Exploration 116117 (2012) 1727

carbonate rocks. High CO2 in the ore uids reacted with limestone
which released Fe 2 + that scavenged the H2S to form pyrite, thus reducing gold solubility and inducing gold precipitation.

would dissolve quartz, rather than deposit quartz. While it may not
be valid for all Nevada gold deposits, at the Pipeline deposit the
uid inclusion gas data suggests that ore uids were likely sourced
from condensing magmatic volatiles.

5. Examples
5.2. The STONE 6 experiment
Fluid inclusion gas analysis is not limited to geothermal systems
and hydrothermal ore deposits. The approach can be applied to a
broad variety of geologic systems where aqueous- or vapordominated inclusions are present. The method is not applicable to
melt inclusions as gases are not liberated from them during the act
of crushing. Several cases from contrasting geologic systems are presented below.
5.1. Nevada gold deposit
The Pipeline gold deposit, Nevada, dated at 92 Ma (Blamey, 2000),
was sourced from magmatic volatiles (Blamey and Norman, 2000).
The CO2/CH4 versus N2/Ar discrimination diagram indicates that meteoric uids are precluded whereas magmatic volatiles were likely
the source of ore uids (Fig. 8a). Furthermore, the Pipeline dataset
from Blamey (2000) was plotted on the CO2/N2 versus total gas discrimination diagram and plots with a condensation slope (Fig. 8b).
Microthermometry measurements by Blamey (2000) conrm that
CO2-rich inclusions have the lowest salinity thus supporting salinity
dilution by condensing uids. Individual samples tend to plot in a
group suggesting that condensation occurred outside the deposit
and that condensed gases subsequently entered the deposit. It is considered unlikely that condensation occurred in the veins where the
quartz was deposited because condensing vapors lack silica and

In an effort to evaluate whether evidence of life would survive


within a meteorite, the STONE 6 experiment involved a Devonian siltstone hosting organic biomarkers subjected to passage through the
Earth's atmosphere, thus simulating a meteorite (Parnell et al.,
2011). Although 3/4 of the sample was ablated, the recovered surface
had melted to a bubble-rich glass on top of a baked siltstone substrate. Mass spectrometry was effective in analyzing the inclusion
gases (Parnell et al., 2011). They showed increases in CO2/CH4 and
total sulfur gases in the glass relative to the original rock (see
Fig. 9). It was interpreted that accessory carbonate had contributed
CO2 whereas ne-grained pyrite had produced SO2 and H2S.
5.3. Serpentinites
In general, hydrated minerals cause vacuum problems in the mass
spectrometer chamber by slowly releasing structural water, thus raising the background. Minerals such as gypsum and jarosite are particularly problematic for the incremental crush method and are best
analyzed by the bulk crush cryogenic separation method. However,
analyzing serpentinites has proved successful with analyses yielding
high hydrogen and methane. Parnell et al. (2010) report gas analyses
by the incremental crush method for a suite of serpentinites, one of
which is Precambrian in age. The analyses support the theory that
the process of serpentinization generates hydrogen and methane,
which are available as energy sources for microbial life. As a result,
Parnell et al. (2010) suggest sampling of serpentinite in the search
for life on Mars.
5.4. Metamorphic inclusions
The composition of metamorphic uid inclusion gases is likely to
be complex as dehydration reactions are controlled by host rock composition, temperature, pressure and equilibrium. It is unreasonable to
assume that a silty limestone will generate the same species during
metamorphism as a carbonaceous shale or weathered arkose. It may
take many years to develop discrimination diagrams for metamorphic
rocks as was done for geothermal systems. However, Wright et al.
(2012) report uid inclusion gases from the Glenstrathfarrar graphite
mine in Scotland where quartzgraphite veins crosscut Proterozoic
(Moinian) medium-grade metapelites. Fluid inclusion gases are

Fig. 8. a. CO2/CH4 versus N2/Ar discrimination plot (template after Norman and Moore,
1999) showing quartz uid inclusion gases from the Pipeline gold mine, Nevada
(slightly modied after Blamey and Norman, 2000). Fluid sources for the uid that deposited quartz plots in the magmatic eld. b. CO2/N2 versus total gas discrimination
plot used to recognize boiling and condensation. The symbols represent individual
quartz samples and data for each sample tend to plot in groups. Quartz uid inclusion
gas data is sourced from the Pipeline gold mine in Nevada (Blamey, 2000) and plot
with a positive slope, corresponding to a condensation slope.

Fig. 9. Cross-plot of (H2S + SO2)/N2 versus CO2/CH4 derived for gas analysis from the
unheated pre-ight control, post-ight heated but not melted sample, and glass with
bubbles generated by passage through the Earth's atmosphere (slightly modied
after Parnell et al., 2010).

N.J.F. Blamey / Journal of Geochemical Exploration 116117 (2012) 1727

25

5.7. Mississippi-Valley-type deposits

enriched in nitrogen which was sourced from ammonium-rich pelitic


rocks from which the veins were sourced. Also, Blamey et al. (2010a)
demonstrated a difference between gas signatures from quartz veins
hosted by quartzites versus pelitic rocks of the Moine Group. Quartz
veins hosted by quartzites had CO2/CH4 ratios above 100 and Ar/He
ratios below 10, whereas quartz veins hosted by metapelites or metamorphosed arenites with a signicant argillaceous component had
CO2/CH4 ratios below 100 and Ar/He ratios above 10 (Fig. 10). The
limited dataset suggests that potassium from clay minerals has contributed to the elevated Ar by the natural decay of 40K to 40Ar. It is
plausible that organic matter associated with clay minerals may be
buffering the CO2/CH4 ratio but further research is required to resolve
this concept.

Fluid inclusion gas data from Mississippi Valley-type (MVT) deposits are reported by Jones and Kesler (1992), Norman et al.
(1985), and Blamey and Norman (2002). Sphalerite from the Daniel's
Harbour deposit in Newfoundland is compared with averages for gas
data reported by Jones and Kesler (1992), the Hansonburg gas data
reported by Blamey and Norman (2002), and gas data from the
Ramah deposit in Labrador (see Fig. 11). Two diverging trends are apparent, one that indicates reduced uids and the second indicating
oxidized uids. The gas data suggests that two contrasting ore deposition models are possible and that it is valuable to apply uid inclusion gas analysis to constrain ore genesis in MVT-type deposits.

5.5. Fault uids

6. Conclusions

Redox is an important ore-forming control at low temperatures


for some metal deposits, particularly where Fe and Mn valence state
changes occur. The change in valence state from a soluble ion under
reducing conditions to an insoluble oxide is characteristic of these deposits. In an example from the Uinta Fault in Utah (Parry and Blamey,
2010), the uids are calculated to have a log aH2 (aq) of 5 to 6
which is sufcient to destabilize hematite. The reducing uids converted the ferric iron to soluble ferrous iron thus bleaching the red
sandstone formations adjacent to the fault by Eq. 5.

Quantitative uid inclusion gas analysis offers a valuable means to


recover uid chemistry information in geothermal systems and hydrothermal ore deposits, in addition to many other geologic environments. Using quantitative gas data or gas ratios it is possible to
discriminate some uid sources (meteoric and magmatic), identify
processes (boiling, condensation, mixing), constrain redox, apply
gas geothermometry, and provide key data for uidrock reaction
modeling. The progressive development of databases and discrimination techniques using uid inclusion gas analysis holds much promise
for the future understanding of uid evolution in the crust.

CH4 4Fe2 O3 16H 10H2 O CO2 8Fe

5.6. Geological glasses


Several geological glasses that are host to bubbles have been analyzed for their volatile content using the incremental crush method
and include Libyan Desert glass, trinitite, impact crater melt, and fulgurite (Blamey and Boslough, 2010; Blamey et al., 2010b). Oxygen is
depleted in all samples. N2/Ar ratios approximate to atmospheric except for the fulgurite where extreme temperatures may have caused
nitrogen-oxide compounds to form. The low CO2 in most samples
does not correlate with oxygen depletion by combustion of carbonaceous material (Blamey and Boslough, 2010) and the authors suggest
that metals associated with an airburst scavenged the atmospheric
oxygen thus matching the model proposed by Boslough and
Crawford (2008).

Fig. 10. Plot of CO2/CH4 versus Ar/He uid inclusion gases for Moine quartz vein samples. Veins hosted in quartzites from Loch Eil1 and Morar1 have CO2/CH4 ratios exceeding 100 and Ar/He ratios that are less than 10. In contrast, quartz veins hosted in pelitic
rocks or those with high argillaceous content from Morar 2, Struy, Glennnan, Glenstrathfarrar and the Basal Pelite have CO2/CH4 ratios less than 100 and Ar/He ratios
greater than 10.

Acknowledgements
Without the pioneering work by the late David Norman, the methodology and interpretation of uid inclusion gas data would never have
advanced to this point and Norman's contribution to this eld of research is acknowledged. Several researchers were involved in the development of the uid inclusion gas analysis methodologies and
include Tom Shepherd, Steve Kesler, Ed Spooner, Gary Landis and
their respective working groups. Some of the early analyses were in
part funded by a DOE grant DE-FG07-00ID13953 to David Norman.
The author wishes to thank Maria Luce Frezzotti and Joe Moore for constructive suggestions during the preparation of this manuscript. Joe
Moore from EGI in Salt Lake City provided many of the geothermal
samples that were analyzed a decade ago. Martin Feely is thanked for
providing a vein sample from Mace Head, Galway. John Parnell provided many samples in addition to constructive suggestions on how to improve the manuscript. Andrew Rankin provided a sample of Nant Helen
quartz thus enabling comparison between mass spectrometry data and
Raman spectroscopy. The stalagmite samples that are used to typify
meteoric uids were provided by Jay Banner and Penny Boston.

Fig. 11. Comparison between Viburnum Trend MVT data generated by Jones and Kesler
(1992) and the author's data for the Hansonburg, Daniel's Harbour and Ramah MVTs?
The Viburnum Trend and Daniel's Harbour gas data indicate reduced uids whereas the
Hansonburg and Ramah data are more oxidized with very similar N2/Ar ratios.

26

N.J.F. Blamey / Journal of Geochemical Exploration 116117 (2012) 1727

James Conliffe kindly provided the sphalerite samples from the Ramah
MVT deposit in Labrador and Daniel's Harbour in Newfoundland. A
very special thanks to Greg Miller of Amec for helping with the setup
of PHREEQC simulations and to Dave Parkhurst of the USGS for making
suggestions to improve the PHREEQC modeling.
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