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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.
18
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.
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.
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
19
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.
Table 1
Lower atmosphere water-free gas composition of selected gases in mole percent
(Mason and Moore, 1982).
N2
O2
Ar
CO2
Ne
He
78.084
20.946
0.934
0.035
0.0018
0.0005
20
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
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.
22
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.
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
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
24
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
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).
25
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.
6. Conclusions
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
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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Brown, P.E., 1989. Flincor a microcomputer program for the reduction and investigation of uid-inclusion data. American Mineralogist 74, 13901393.
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Crushing-cell, Capillary Column Gas Chromatography of Petroleum Fluid Inclusions:
Method and Application to Petroleum Source Rocks, Reservoirs, and Low Temperature Hydrothermal Ores (Abstract): American Current Research on Fluid Inclusions, Socorro, NM, Program and Abstracts (unpaginated).
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Baker, E.T., Massoth, G.J., Lupton, J.E., Walker, S.L., Greene, R.R., Soong, C.W.R.,
Ishibashi, J., Lebon, G.T., Bray, C.J., Resing, J.A., 2005. Evolution of a submarine
magmatichydrothermal system: Brothers volcano, southern Kermadec arc, New
Zealand. Economic Geology 100, 10971133.
Dilley, L.M., 2009. Fluid inclusion stratigraphy: a new method for geothermal reservoir
assessment. Unpublished Ph.D. dissertation, New Mexico Tech, pp. 161.
Dilley, L.M., Norman, D.I., Berard, B., 2004. Fluid inclusion stratigraphy: New method
for geothermal reservoir assessment preliminary results. Proceedings: Twentyninth Workshop of Geothermal Reservoir Engineering, Stanford University, Stanford,
California, January 2628, 2004, pp. 255261.
Gallagher, V., Feely, M., Hogelsberger, H., Jenkin, R.G.T., Fallick, A.E., 1992. Geological,
uid inclusion and stable isotope studies of Mo mineralization, Galway Granite,
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George, S.C., Volk, H., Ahmed, M., 2007. Geochemical analysis techniques and geological applications of oil-bearing uid inclusions, with some Australian case studies.
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mitigation of volcano hazards, pp. 221256.
Goldstein, R.H., Reynolds, T.J., 1994. Systematics of uid-inclusions in diagenetic minerals. SEPM Short Course, 31, p. 199.
Graney, J.R., Kesler, S.E., 1995. Factors affecting gas-analysis of inclusion uid by quadrupole mass spectrometry. Geochimica et Cosmochimica Acta 59, 39773986.
Graney, J.R., Kesler, S.E., Jones, H.D., 1991. Application of gas-analysis of jasperoid inclusion uids to exploration for micron gold deposits. Journal of Geochemical Exploration
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systems. Reviews in Economic Geology 2, 267.
Jones, H.D., Kesler, S.E., 1992. Fluid inclusion gas chemistry in east Tennessee Mississippi
Valley-type districts: evidence for immiscibility and implications for depositional
mechanisms. Geochimica et Cosmochimica Acta 56, 137154.
Jones, D.M., McLeod, G., 2000. Molecular analysis of petroleum in uid inclusions: a
practical methodology. Organic Geochemistry 31, 11631173.
Kesler, S.E., Haynes, P.S., Creech, M.Z., Gorman, J.A., 1986. Application of uids inclusion
and rockgas analysis in mineral exploration. Journal of Geochemical Exploration
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Landis, G.P., Hofstra, A.H., 1991. Fluid inclusion gas chemistry as a potential minerals
exploration tool case studies from Creede, CO, Jerrit Canyon, NV, Coeur-dalene
District, ID and MT, southern Alaska mesothermal veins, and midcontinent MVT's.
Journal of Geochemical Exploration 42, 2559.
Landis, G.P., Snee, L.W., Juliani, C., 2005. Evaluation of argon ages and integrity of uidinclusion compositions: stepwise noble gas heating experiments on 1.87 Ga alunite
from Tapajs Province, Brazil. Chemical Geology 215, 127153.
Mason, B., Moore, C.B., 1982. Principles of Geochemistry, Many Analyses and Discussion on Composition of Air and Water Bodies4th Edition. Wiley.
Moon, K.J., 1991. Application of uid inclusions in mineral exploration. Journal of
Geochemical Exploration 42, 205221.
Moore, J.N., Powell, T.S., Heizler, M.T., Norman, D.I., 2000. Mineralization and hydrothermal history of the Tiwi geothermal system, Philippines. Economic Geology
95, 10011023.
Moore, J.N., Norman, D.I., Kennedy, B.M., 2001. Fluid inclusion gas compositions from
an active magmatic hydrothermal system: a case of The Geysers geothermal eld,
USA. Chemical Geology 173, 330.
Munz, I.A., 2001. Petroleum inclusions in sedimentary basins: systematics, analytical
methods and applications. Lithos 55, 195212.
Nehring, N.L., D'Amore, F., 1984. Gas chemistry and thermometry of the Cerro Prieto,
Mexico, geothermal eld. Geothermics 13, 7589.
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Norman, D.I., Blamey, N.J.F., 2001. Quantitative gas analysis of uid inclusion volatiles
by a two mass spectrometer system. European Current Research on Fluid Inclusions, No. XVI, Porto, Portugal, Abstracts, pp. 341344.
Norman, D.I., Moore, J.N., 1997. Gaseous species in uid inclusions: a uid tracer and
indicator of uid processes. European Current Research on Fluid Inclusions, No.
XIV, Nancy, France, Abstracts, pp. 243244.
Norman, D.I., Moore, J.N., 1999. Methane and excess N2 and Ar in geothermal uid inclusions. Proceedings: Twenty-fourth Workshop of Geothermal Reservoir Engineering,
Stanford University, Stanford, California, January 2224, 1999, pp. 233240.
Norman, D.I., Moore, J.N., 2003. Organic species in geothermal waters in light of uid
inclusion gas analyses. Twenty-eighth Workshop on Geothermal Reservoir Engineering,
pp. 96103.
Norman, D.I., Musgrave, J.A., 1994. N2ArHe compositions in uids inclusions: indicators of uid source. Geochimica et Cosmochimica Acta 58, 11191131.
Norman, D.I., Sawkins, F.J., 1987. Analysis of volatiles in uid inclusions by mass spectrometry. Chemical Geology 61, 110.
Norman, D.I., Ting, W., Putnam, B.R., Smith, R.W., 1985. Mineralization of the Hansonburg Mississippi-Valley-type deposit, New Mexico: insights from composition of
gases in uid inclusions. The Canadian Mineralogist 23, 353368.
Norman, D.I., Harrison, R.W., Andres, C.B., 1991. Geology and geochemical analysis of
mineralizing uids at the St-Cloud and United-States Mines, Chloride mining district,
New Mexico. Journal of Geochemical Exploration 42, 6189.
Norman, D.I., Chomiak, B.A., Moore, J.N., 1998. Approaching equilibrium from the hot
and cold sides in the FeS2FeSFe3O4H2SCO2CH4 system in light of uid inclusion gas analysis. In: Arehart, G.B., Hulston, J.R. (Eds.), WaterRock Interaction. A
Balkema Publishers, pp. 565568.
Norman, D.I., Blamey, N.J.F., Moore, J.N., 2001. Overabundance of gaseous species and
the source of organic compounds in geothermal uids. Proceedings, TwentySixth Workshop on Geothermal Reservoir Engineering Stanford University, Stanford,
California, January 2931, 2001, pp. 234242.
Norman, D.I., Blamey, N.J.F., Moore, J.N., 2002a. Interpreting geothermal processes and
uid sources from uid inclusion organic compounds and CO2/N2 ratios. Proceedings, Twenty-Seventh Workshop on Geothermal Reservoir Engineering. Stanford
University, Stanford, California, pp. 266274.
Norman, D.I., Blamey, N.J.F., Kurilovich, L., 2002b. New applications of geothermal gas
analysis to exploration. Transactions Geothermal Research Council 26, 345353.
Parkhurst, D.L., Appelo, C.A.J., 1999. User's Guide to PHREEQC (Version 2) A Computer Program for Speciation, Batch-reaction, One-dimensional Transport, and Inverse
Geochemical Calculations. USGS Water-Resources Investigations Report 99-4259.
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Stefnsson, A., Seward, T.M., 2004. Gold(I) complexing in aqueous sulphide solutions
to 500 C at 500 bar. Geochimica et Cosmochimica Acta 68, 41214143.
Takenouchi, S., 1991. Fluid inclusion gas-composition of some mineral deposits and a
geothermal area. Journal of Geochemical Exploration 42, 107132.
Velador, J., 2010. Timing and origin of intermediate suldation epithermal veins and
geochemical zoning in the Fresnillo District, Mexico: constrained by 40Ar/39Ar geochronology, uid inclusions, gas analysis, stable isotopes, and metal ratios. Unpublished Ph.D. dissertation, New Mexico Tech, pp. 170.
Walder, I.F., Norman, D.I., Segalstad, T.V., 1991. Fluid inclusion gas analysis of hydrothermal vein molybdenum deposits associated with the Drammen granite in the
Permian Oslo Rift, Norway. Journal of Geochemical Exploration 42, 195203.
Wilkins, R.W.T., Jenatton, L., 1991. Multichannel micro-Raman spectroscopy of uid
inclusion gases in mineral exploration. Journal of Geochemical Exploration 42,
157166.
Wright, A.J., Blamey, N.J.F., Conliffe, J., Costanzo, A., Parnell, J., 2012. Origin of veingraphite derived from metamorphic uids in Moine (Glennnan Group) rocks,
NW Scotland. Scottish Journal of Geology 48, 114.
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