Physical-Chemical Properties and Metal Budget of Au-Transporting Hydrothermal Fluids in Orogenic Deposits

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Physical-chemical properties and metal budget of Au-transporting

hydrothermal fluids in orogenic deposits
PAOLO S. GAROFALO1*, MATTIAS B. FRICKER2, DETLEF GÜNTHER2,
DANILO BERSANI3 & PIER PAOLO LOTTICI3
1
Department of Earth and Environmental Sciences, University of Bologna, Italy
2
Trace Element and Microanalysis Group, ETH Zürich, Switzerland
3
Department of Physics and Earth Sciences, University of Parma, Italy
*Corresponding author (e-mail: paolo.garofalo@unibo.it)
Abstract: We use a set of analytical techniques for fluid inclusion analysis to determine the bulk
properties of the ore fluids from five orogenic gold deposits. The most common ore fluid is a low
salinity (0.4– 6.5 wt% NaCl) two- to three-phase aqueous-carbonic fluid. Its T h(total) range is
200–400 8C, and total homogenization occurs by bubble or liquid disappearance. A less com-
mon aqueous fluid of similar bulk salinity and T h(total) is also documented. Microchemical data
show that the ore fluid in the five deposits is chemically uniform and made of Na, subordinate K and
B and minor to trace amounts of Cu, As, Li, Sr, Rb, Ba, Cs, Sb and Au (range 0.5– 5 mg/g). Ther-
modynamic modelling carried out for one of the studied deposits indicates that the ore fluid was in
equilibrium with vein minerals at the time of gold deposition, and that its vapour phase was dis-
tinctly enriched in Au, B, As and Sb. The proposed mechanism of gold precipitation is a combi-
nation of fluid decompression and boiling. Combining these results with 3D geometrical
reconstructions of one of the studied deposits (Sigma), we estimate that a minimum ore fluid
volume of c. 0.1–1.0 km3 is sufficient to generate a world-class orogenic deposit.
Orogenic deposits provide about a third of the belts, with gold precipitation being syn- to post-
global gold production (Goldfarb et al. 2001; metamorphic in age; (5) relatively low sulphide
Frimmel 2008). These deposits are formed within abundance within the veins; (6) carbonate-sericite-
active continental margins in orogenic belts where albite-sulphide hydrothermal alteration of host
major tectonic boundaries juxtapose metamor- rocks postdating metamorphism; (7) poorly devel-
phosed volcanic-plutonic and sedimentary terranes. oped mineral and metal zoning within the ore
The ore bodies consist of Au-mineralized vein net- bodies; and (8) genesis from low to moderate
works filled with quartz, carbonates and other sili- salinity ore fluids over a large temperature range
cates that in places crosscut the stacked terranes of (250 –700 8C), but mostly within 300–350 8C.
the continental margins. The veins are dilated por- These common traits occur systematically in depos-
tions of vertically extensive brittle-ductile to ductile its from different terrains having distinct ages,
fracture networks that form due to the advection of suggesting that a common geological process and
aqueous hydrothermal fluids within the continen- Au-transporting fluid are responsible for their
tal crust (Ridley et al. 1996; Groves et al. 2003). formation.
These ore fluids are generated in still undefined Here, we present a database of fluid inclusion
source regions deep in the crust and transported to properties from five typical orogenic deposits,
shallower levels (3–15 km depth) through the vein which show most of the geological characteris-
networks along which they deposit gold. A number tics listed above. The database was constructed
of studies (Kerrich et al. 2000; Ridley & Diamond with the aim of determining as accurately as poss-
2000; Groves et al. 2003) showed that although ible the properties of the Au-transporting fluid in
these networks do not occur systematically in all this geological environment. In particular, Laser
orogens, they have a set of important geological Ablation-Inductively Coupled Plasma-Mass Spec-
features in common, which include: (1) formation trometry (LA-ICP-MS) of single fluid inclusions
during accretionary orogenic events; (2) occurrence paragenetically coeval with vein gold provides the
relatively close to regional tectonic lineaments, concentration of a suite of metals (including Au)
especially along lower-order splays of these struc- in this fluid. This dataset, when combined with 3D
tures; (3) spatial association with granitoid intru- geometrical reconstructions of one of these deposits,
sions; (4) occurrence within some metamorphic offers new constraints on the volume of the ore
From: Garofalo, P. S. & Ridley, J. R. (eds) 2014. Gold-Transporting Hydrothermal Fluids in the Earth’s Crust.
Geological Society, London, Special Publications, 402, 71– 102.
First published online April 3, 2014, http://dx.doi.org/10.1144/SP402.8
# The Geological Society of London 2014. Publishing disclaimer: www.geolsoc.org.uk/pub_ethics
Downloaded from http://sp.lyellcollection.org/ at CAPES-UNIVERSIDADE FEDERAL DE MINAS
72 P. S. GAROFALO ET AL.
fluid involved in the formation of these networks, the granite and plagiogranite dykes at high angle.
which might be helpful for the definition of future Other coeval Au-bearing quartz-carbonate veins
genetic models. crosscut the sedimentary and igneous sequence.
The ore bodies are made of en-echelon arrays of
gold veins that are individually discontinuous
The studied deposits along strike and contain relatively large euhedral
crystals. Other vein minerals are pyrite, scheelite,
The five studied deposits occur in different orogenic galena, chalcopyrite, aikinite (PbCuBiS3), tennan-
belts and formed at different times from the Late tite-tetrahedrite and native gold.
Archaean to the Tertiary. They are the Berezovs- Hydrothermal alteration adjacent to individual
koye deposit from the Central Urals (Baksheev veins can be as much as 1.5 m in thickness. The
et al. 2001), Sigma from the Abitibi greenstone acid-intermediate igneous host rocks are altered
belt of Canada (Robert et al. 1995), Kanowna-Red to an assemblage of quartz, K-feldspar, calcite,
Hill from the Yilgarn craton of Western Australia dolomite, sericite, pyrite and scheelite. The mafic-
(Groves et al. 1990; Stanton-Cook 1992), Pestarena intermediate host rocks are altered to chlorite,
from the Monte Rosa district of the western Italian epidote, amphibole, albite, quartz, tourmaline, car-
Alps (Lattanzi et al. 1989) and Wattle Gully from bonates and hematite. The ultramafic host rocks
the Lachlan Fold Belt of Australia (Cox 1995). are altered to talc, magnesite, fuchsite and hematite.
The vertical extent of these deposits (and hence The age of the hydrothermal alteration was esti-
their economic relevance) is extremely variable, mated from Sm/Nd isotope dating of scheelite at
and so is the wall rocks hosting the veins and the 347 + 12 Ma (Baksheev et al. 2002).
proportions of silicate, carbonates and sulphides
in the ore bodies. These variable characteristics cor- The Sigma deposit
respond in principle to the largest possible range
of ore fluid properties for this class of deposits. In The Sigma deposit occurs within the Val d’Or dis-
the paragraphs below, we briefly summarize the trict; a region of the southeastern margin of the
geological histories of these deposits and report Archaean Abitibi greenstone belt of Canada domi-
on the analytical techniques used to construct the nated by ultramafic to felsic metavolcanics rocks.
database. We then show how the new dataset In this region, a ductile to brittle-ductile fault zone
improves the present knowledge of Au-transporting of regional importance, the Larder Lake-Cadillac
orogenic fluids. fault zone, separates the Archaean rocks of the
Abitibi to the north from metasedimentary rocks
The Berezovskoye deposit of the Pontiac Subprovince to the south (Robert
1994). Sigma and neighbouring orogenic depos-
With a mine history longer than 250 years and a its belong to a group of approximately 40 vein
total production exceeding 130 t (Gosselin & Dubé deposits of the Abitibi belt characterized by the pre-
2005), the giant Berezovskoye gold deposit is sence of tourmaline as a major vein mineral. The
located in the Central Urals, specifically within a deposit consists of a vertically extensive network
thick Silurian-Devonian succession of volcaniclas- of shear veins and associated subhorizontal exten-
tic/terrigenous and mafic/ultramafic rocks called sion veins that crosscut a sequence of steeply dipp-
the Sverdlovsk tectonic zone (Baksheev et al. ing andesitic volcanics, porphyritic diorite and
2001, and ref. therein). This is a complex stratified feldspar porphyry dykes, and extends further to
sequence with igneous rocks forming sheets and the south into the neighbouring Lamaque deposit
laccoliths within a sedimentary sequence. In the (Robert & Brown 1986a). Together, the Sigma
ore field, this sequence is gently folded to the West and Lamaque vein networks make a single world-
and Northeast at angles of 20 –308, and its central class gold deposit (Groves et al. 2003) that produced
part is intruded by the 355 –350 Ma bodies form- c. 360 t of gold (Gosselin & Dubé 2005). In the two
ing the porphyritic granite of the Shartash pluton. networks the characteristics of the ore bodies show
In this area, strictly associated with the pluton and some differences. At Sigma the network has a
veins, is a swarm of north–south-trending, closely- minimum vertical dimension of 1.8 km, while at
spaced porphyritic dykes of plagiogranite, grano- Lamaque exploitable mineralization is restricted to
diorite and lamprophyre, which are continuous for a depth of approximately 1.2 km (Garofalo et al.
kilometres along strike. The age of these dykes 2002). Porphyritic diorite intrudes the volcanic
was estimated with K/Ar and Rb/Sr isotope dat- rocks at Sigma and is preserved as characteristi-
ing to be between 315 Ma and 355 Ma (Sazonov cally elliptical bodies that resulted from shear-
et al. 2001). ing and transpositional folding. The proportion of
The ore bodies with the highest gold grades are this diorite increases steadily with depth, and feld-
south dipping ladder quartz-carbonate veins cutting spar porphyry dykes crosscut both the diorite and
AU-TRANSPORTING HYDROTHERMAL FLUIDS 73
the intruded volcanics forming a network of con- Quartz and tourmaline occupy more than 95%
jugate steeply dipping tabular bodies. At Lamaque of vein volume at Sigma, with calcite, scheelite,
the ore bodies are associated mostly with three albite, K-feldspar, sericite, biotite, chlorite, epidote,
late tectonic tonalite-diorite plugs (Latulippe 1976; apatite, pyrite, pyrrhotite, chalcopyrite and gold
Daigneault 1983; Burrows & Spooner 1989), present as minor phases. Combining the network
which were dated at c. 2685 Ma by U/Pb iso- volume with the estimation of tourmaline abun-
tope analyses of hydrothermal rutile and titanite dance in the veins, Garofalo et al. (2002) calculated
(Jemielita et al. 1989). that 2.1 × 106 m3 of tourmaline and 3.2 × 106 m3
The shear veins at Sigma form a network of of quartz precipitated at Sigma during Au deposi-
anastomosing veins within south dipping shear tion. Below, we show that these estimated masses
zones. Hydrothermal zircons yield a U/Pb age of of vein minerals are fundamental constraints for
2682 + 8 Ma (Claoué-Long et al. 1990). This age the volume of ore fluid that formed the deposit.
overlaps that of regional metamorphism (2684 + Visible hydrothermal alteration (bleaching)
7 Ma; Wong et al. 1991) and of the Lamaque around the quartz-tourmaline veins is intense at
tonalite, indicating that late-tectonic magmatism, Sigma, and forms 5–50 cm wide haloes of albite-
regional metamorphism and vein formation all carbonate-pyrite-pyrrhotite. This alteration was
occurred within a time period of a few million the object of several detailed studies (Robert &
years in the area. Brown 1984, 1986b; Dubé et al. 1987; Garofalo
Gold-rich subhorizontal extension veins occur 2004a, b). Garofalo (2004a, b) showed that tourma-
commonly at, or close to, the tips of segments of line-calcite-quartz-pyrite-pyrrhotite type alteration
steep veins both at Sigma and Lamaque and are accompanied gold precipitation.
characterized by open-space filling textures. Dimen-
sions and thickness of subhorizontal veins decrease The Kanowna-Red Hill deposit
with depth, and those deeper than c. 950 m are so
small that mining is sub economic. A reconstruction Discovered in 1989 and mined since 1993, the
of the 3D geometry and gold grade distribution of Red Hill deposit occurs within the Kanowna min-
the shear veins from a representative sub volume ing camp of the Eastern Goldfield Province (Yilg-
of the deposit (Garofalo et al. 2002) showed that arn Craton), which includes a cluster of small vein
the Sigma network is made of few veins with a deposits and the large Kanowna Belle mine (Groves
large vertical dimension (typically .100 m) and a et al. 1990). The deposit produced more than 125 t
large number of vertically short veins. The highest of Au (Table 1).
gold grades occur at the interconnections between The geology of Red Hill consists of a sequence
the large veins and small vertical splays or sub- of mafic and ultramafic lavas with felsic volcanics,
horizontal extension veins, showing the important sediments and conglomerates of the Gindalbie For-
role of fracture intersection for fluid flow and mation, which is akin to the Black Flag Beds of the
gold precipitation. neighbouring Golden Mile deposit of Kalgoorlie
Table 1. Summary of previous fluid inclusion data from the studied deposits*
Deposit Deposit Au (t) Main ore fluid CO2 concentration Microthermometry Trapping
Age (Ma)
21
XCO2 m kg sol Mass Mass% T h(total)\8C T\8C
% NaCleq P\MPa
Berezovskoye1 347 + 12 130† H2O –NaCl –CO2 3.1 – 5.3 2.4 –14.1 270–365 270–365
150–350
2 3
Pestarena 29 19.5 H2O –NaCl –CO2 0.08 7 300–350 400–450
(L and C) 100–150
Red Hill/ 2640–2620 128.5† H2O –NaCl –CO2 10 –40 1.7 –4.0 200–315 280–320
Kanowna4 (L and V) 180–320
Sigma5, 6 2682 + 8 358.2† H2O –NaCl –CO2 –CH4 0.13 –0.59 1.0 –6.0 210–425 320–450
(L and V) 200
7 †
Wattle Gully c. 440 12.9 H2O –NaCl –CO2(– CH4) 0.05 –0.2 280–310 300
80–175
*Data is from: (1) Baksheev et al. (2001); (2) Lattanzi et al. (1989); (3) Pettke et al. (1999); (4) Ho et al. (1990); (5) Robert & Brown (1986a); (6) Robert et al.
(1995); and (7) Cox et al. (1995). CO2 concentration is reported as molar fraction, moles per kg of solution, and mass per cent. T h (total) values give the ranges of
total homogenization temperatures. Reported modes of total homogenization are given in brackets, and refer to bubble disappearance (L), liquid disappearance
(V), or critical homogenization (C).
†
Sum of production and reserves for each deposit from the World Compilation table of Gosselin & Dubé (2005). Data on Au resources from Pestarena compiled
from historical documentation on mine production available at ‘Museo Storico dell’Oro Italiano’, Predosa (Al), Italy. This figure likely underestimates the total
Au resources because of poor historical documentation before year 1810.
(Stanton-Cook 1992). Red Hill is hosted by an unde- facies assemblages because different sections of
formed felsic porphyry stock having a size of the subducting wedge were dragged to different
c. 1 × 1 km within the camp and intruding the sedi- depths and then exhumed. This results in dia-
mentary sequence. It is made of a set of shallowly chronous peak metamorphic ages within the wedge
to moderately dipping quartz fissure veins hosted (Desmons et al. 1999). After collision (i.e. since
by the stock in which volumes of large and euhed- Late Eocene –Early Oligocene), the subduction-
rally terminated quartz is found. The locations of related metamorphic regime of the wedge changed
the veins are clearly controlled by the geometry of into a regime of regional metamorphism, which
the Fitzroy Fault, a mostly planar fault of great caused the metamorphic re-equilibration of the pre-
importance for the belt (Stanton-Cook 1992). The vious assemblages into greenschist (Aosta Valley-
ore shoots consist of vein arrays occurring within Valais) to amphibolite facies (Val d’Ossola-Tessin)
breccias that strike NW –SE and dip 258 to the mineral assemblages (Desmons et al. 1999).
NE. The richest ore shoots, which are controlled The main regional metamorphic event at Pest-
by fault intersections, have strike and dip lengths arena peaked at c. 38 Ma. The local geology is
ranging from hundreds of metres to kilometres, controlled by a major ENE –WSW trending back
widths of 0.5–10 m and they postdate regional fold, the late Alpine Vanzone anticline (Bistacchi
metamorphism. & Massironi 2000), which deforms the earlier
The deposit contains widespread and variable metamorphic isograds. Field data show that the
carbonate-sericite alteration and minor silicifica- Au-bearing veins of Pestarena were emplaced into
tion. Pyrite is variably disseminated within host various host rocks during, or shortly after, the
rocks and occasionally occurs in veins. It comprises formation of the Vanzone anticline (Lattanzi et al.
between 1% and 5% of the rock by weight and is 1989). Their age was determined to be 29 + 0.2
generally associated with gold mineralization. Chal- Ma by 40Ar/39Ar dating of hydrothermal vein
copyrite, galena, pyrrhotite, scheelite, sphalerite, micas (Pettke et al. 1999). The veins crosscut
stibnite and tellurides are present in the ore bodies, all the local lithotypes of the nappe, i.e. micaschist,
but their volumetric abundance is minor (,0.1 paragneiss, orthogneiss and metagranite, and exhibit
vol% combined). Gold mineralization occurs with distinct styles in each rock (Lattanzi et al. 1989, and
the disseminated pyrite and is occasionally visible ref. therein).
with the naked eye. The bulk of the 5-mg/g grade Vein mineralogy is dominated by quartz, with
Au mineralization is associated with fine net- subordinate carbonates, sericite, chlorite, tourma-
works described as crackle breccias with sericite- line, rutile, apatite and amphibole (Lattanzi et al.
carbonate alteration and variable silicification. 1989). Opaque minerals are typically pyrite and
arsenopyrite, with minor proportions of pyrrhotite,
The Pestarena deposit sphalerite, galena, chalcopyrite and tetrahedrite.
Gold is invariably associated with the sulphides,
Pestarena is located in the Upper Ansasca valley mainly with pyrite and galena. Hydrothermal altera-
of the Western Alps (Novara Province, Italy) and tion of the wallrock, which is more evident in the
is characterized by a documented historical produc- orthogneiss than in the paragneiss, is evident from
tion of c. 20 t (Pipino 2010, pers.comm.), which the replacement of metamorphic garnet and bio-
makes it the economically most important orogenic tite by an assemblage made of chlorite, sericite
gold deposit of the Monte Rosa district. Several and quartz (Lattanzi et al. 1989).
ore bodies were mined at Pestarena since at least
the year 1650, but all of them terminated their oper- The Wattle Gully deposit
ations in the early 1960s.
The gold-bearing quartz veins of Pestarena occur The Wattle Gully deposit is a classic example of a
within the Monte Rosa nappe, a unit of the Penninic fault-hosted gold deposit of the Bendigo-Ballarat
domain of the Alpine orogeny. Regional geology zone of the Lachlan fold belt (Victoria gold pro-
is dominated by the presence of stacks of tectonic vince, Australia). It has produced c. 13 t of gold
nappes that accreted before and during the Alpine (Gosselin & Dubé 2005), which makes it one of
orogeny and built a Europe-vergent Austroalpine- the most important vein systems of the ore field
Penninic orogenic wedge (Bistacchi & Massironi (Cox et al. 1995). The deposit is located within a
2000; Dal Piaz 2001). This wedge formed initially belt of Ordovician quartz-rich turbidites and slates
in a low-temperature high pressure metamorphic having a total stratigraphic thickness of c. 2 km.
regime during subduction of the Mesozoic Pied- The belt forms trains of regular north–south trend-
mont Ocean beneath Adria, with eclogite facies ing folds, which are mechanically associated with
peak metamorphic conditions in the Monte Rosa high-angle reverse faults that localize the gold
nappe (Bistacchi & Massironi 2000, and refs deposits. Gold-mineralized faults are east- and
therein). Adjacent nappes do not record eclogite west-dipping, strike approximately parallel to the
fold axes, and formed during the late stages of The fluid inclusion data are summarized in
regional crustal shortening (Cox et al. 1995, and Table 1 and are in line with those reported in the
ref. therein). 40Ar/39Ar dates of white mica from global compilation of Ridley & Diamond (2000).
faults in the province indicate that gold mineraliz- The main ore fluid in these deposits is unanimously
ation was episodic between 460 Ma and 440 Ma considered to be entrapped within aqueous-carbonic
(Bierlein et al. 1999). (H2O –NaCl–CO2) fluid inclusions, which contain
The Wattle Gully mine is hosted by lower Ordo- minor CH4. The bulk salinity of this fluid is
vician turbidites, and consists of a set of Au-bearing between 2 mass% and 14 mass% NaCleq, CO2
quartz veins within a west-dipping reverse fault varies from 8 mol% to 60 mol% and the tempera-
zone, which cuts an anticline-syncline pair. The ture of total homogenization is between c. 200 8C
geometry of this fault zone is strongly influenced and 400 8C. The trapping conditions of this fluid
by the local fold geometry, and at depth it is concor- in the five deposits were estimated to be in the
dant with the west-dipping limb of the anticline. range of 270–450 8C and 100–350 MPa (Table
Geometry and volume of the Au-bearing fault 1). Phase separation of this fluid was considered
zone is controlled by the coalescence of bedding- an important mechanism of gold deposition.
concordant and bedding-discordant segments of A second type of orogenic ore fluid is the aque-
the faults, which form three en-echelon dilatant ous (H2O –NaCl) type of fluid inclusions hosted
jog domains that extend 600 m along strike and within vein quartz, which was reported in all depos-
300 m down dip (Cox et al. 1991). Ore bodies are its except that at Berezovskoye. This fluid makes
made of many discontinuous and irregular quartz in general a small proportion of the entrapped vein
lodes and associated subhorizontal extension fluid (with the exception of Wattle Gully: Cox
veins, some of which show a typical crack-seal 1995), and its time relationship with the aqueous-
texture. Quartz veins contain less than 5 vol% of carbonic fluid and with Au precipitation is not
ankerite, dolomite, sericite, chlorite, pyrite, arseno- always clear (Lattanzi et al. 1989; Ho et al. 1990).
pyrite, sphalerite, galena, chalcopyrite and pyrrho- The aqueous inclusions show bulk salinities below
tite. Gold occurs mainly within the veins and is 7 mass% NaCleq (although at Sigma a much wider
associated with sulphides where the veins are interval of 4– 30 mass% NaCleq was reported;
enclosed by slates. In contrast, when the veins are Robert et al. 1995; Boullier et al. 1998) and a
hosted by the arenitic turbidites, gold is quartz broad range of temperatures of total homogeniz-
hosted and coarser in size (Cox et al. 1991). Hydro- ation between 50 8C and 370 8C. Only at Sigma
thermal alteration adjacent to the veins is limited in and Red Hill was aqueous fluid considered an
extent and intensity and consists mainly of arseno- integral part of the main mineralization events,
pyrite, sphalerite, pyrrhotite, chalcopyrite and but with some important restrictions. At Sigma, a
carbonate disseminations. detailed field-based study demonstrated that only
aqueous inclusions having temperatures of total
homogenization higher than 250 8C were related
Previous fluid inclusion studies with Au deposition (Boullier et al. 1998). This
important result implies that any textural associa-
Several fluid inclusion studies were carried out on tion between gold and aqueous fluids should be
the deposits studied here (Robert & Kelly 1987; interpreted with extreme caution. The aqueous
Lattanzi et al. 1989; Ho et al. 1990; Cox et al. fluid was interpreted as an end-member product
1995; Robert et al. 1995; Baksheev et al. 2001; of unmixing of a parent low salinity ore fluid of
Olivo et al. 2006) or in neighbouring deposits aqueous-carbonic composition.
sharing the same geological history (Diamond A third type of ore fluid was documented at
1990). Some of these studies provided the first sets Berezovskoye, Sigma and Wattle Gully and con-
of fluid inclusion data from orogenic deposits and sisted of CO2 dominant single- and two-phase
significantly influenced the genetic models pro- inclusions (liquid-vapour, with volume fractions of
posed in the following years. They determined ore the vapour phase exceeding 40%). These inclu-
fluid properties by combining microthermomet- sions are quite rare within the Wattle Gully veins
ric determinations with data from other analytical (Cox 1995) but are abundant at Sigma where they
techniques, mostly Raman spectroscopy and crush- make between 15% and 75% of the fluid inclu-
leach analyses. Additional independent constraints sions (Robert et al. 1995). Carbon-dioxide-rich
on fluid properties were provided by the oxygen inclusions have negative crystal or smoothly cur-
and carbon isotope composition of quartz (Lattanzi ved shapes, occur in trails or isolated clusters, and
et al. 1989; Cox 1995; Baksheev et al. 2001), are associated with the aqueous-carbonic inclu-
carbonate, scheelite and tourmaline from the ore sions. At Wattle Gully a maximum XH2O of 0.4
bodies (Baksheev et al. 2001) and by mineral and variable CO2/CH4 molar ratios were estimated
geothermometres (Lattanzi et al. 1989). for these inclusions. At Sigma the CO2 melting
temperatures was determined to be between –63 8C This limitation is partly due to the fact that parage-
and –56 8C and total homogenization between netic relationships between Au deposition and
–49 8C and +31 8C (Robert & Kelly 1987; Robert fluid entrapment are subjected to a degree of
et al. 1995). These inclusions were interpreted at interpretation.
Sigma as batches of ore fluid entrapped within the Another limitation of the current database is
Au veins after unmixing during significant fluc- represented by the determination of the ore fluid
tuations of fluid pressure (Robert et al. 1995), but composition with the bulk crush-leach extraction
at Wattle Gully as an end-member fluid unmixed technique (Yardley et al. 1993; Baksheev et al.
from a parent aqueous-carbonic ore fluid (Cox 2001). This method utilizes bulk samples of rela-
et al. 1990). tively large size, which may contain multiple
While representative of a number of ore depos- groups of fluid inclusions, some of which are poten-
its worldwide, these fluid inclusion data pro- tially unrelated with Au deposition. In-situ analy-
vide incomplete constraints for bulk properties and sis of solutes by LA-ICP-MS of individual fluid
genetic processes of the ore fluids. The most evident inclusions, which is used in this study, overcomes
lack of data involves the aqueous fluid, whose prop- many of the uncertainties inherent in bulk crush
erties need to be defined precisely. Another poorly leach (Günther et al. 1998; Pettke et al. 2012).
resolved question concerns the conditions of fluid
unmixing within the veins and the identity of
the end-member fluids. As suggested by Lattanzi Methods
et al. (1989) and Cox et al. (1995), unmixing of Sampling and analysis rationale
a low salinity parent ore fluid in a temperature
range of c. 200 –300 8C would generate aqueous- Table 2 lists the set of samples selected for fluid
carbonic- and CO2-rich end-member fluids similar inclusion analysis. Most of these samples were
to those found at Pestarena and Wattle Gully. collected at productive underground stopes of the
Thus, the genesis of the high-salinity aqueous fluid deposits, although a few of them are from surface
remains open. outcrops and diamond drill holes. Four samples
A third undefined question concerns the role from Sigma have been collected from a deep
played by post-entrapment modification in the defi- drill hole and from Au-rich underground exposures
nition of the ore fluid properties listed above. Exper- that together extend over a vertical interval of
imental data show that the range of post-entrapment c. 1300 m, and north– south and east –west sections
modifications of fluid inclusions resulting from of c. 540 and 850 m, respectively. The deposit vol-
plastic and brittle deformation of the host quartz ume containing these samples is representative of
have potential affects on the bulk composition of a large subset of the entire Sigma network (Garofalo
entrapped fluids (Vityk & Bodnar 1995, 1998; et al. 2002). The Sigma-Audet sample (Table 2) is
Bodnar 2003b; Diamond et al. 2010). Because a surface sample from a quartz-tourmaline vein
these types of deformation are well documented outcropping five km east of the Sigma mine. That
in orogenic deposits (Garofalo et al. 2005; e.g. vein represents a good case of a barren, shear-hosted
Ridley & Hagemann 1999), it is highly probable quartz-tourmaline vein identical to the most pro-
that the interpretation of fluid inclusion data spective Au-rich veins of the Val d’Or district
should somehow consider re-equilibration effects. (Garofalo 2000).
For instance, the interpretation whereby at Sigma Other Au-rich samples are two euhedral quartz
the large compositional ranges of the three ore crystals from Au-bearing veins of the Berezovskoye
fluids reflect entrapment of batches of unmixing deposit (both veins crosscutting the igneous host
ore fluids during fluid pressure fluctuations from rock) and two samples from the quartz networks
lithostatic to lower values (Robert et al. 1995) of Red Hill and Wattle Gully deposits of Australia
should be critically evaluated. Such an evaluation (Table 2), which crosscut a hydrothermally-altered
is possible when fluid inclusion properties are sin- dacitic porphyry and a sequence of black shales
gled out from a statistically representative group of and slates, respectively. The samples from the his-
co-genetic fluid inclusions within minerals (Fluid torical Pestarena deposit have been studied pre-
Inclusion Assemblage (FIA); cf. Vityk & Bodnar viously and showed the presence of gold grains
1995; Vityk et al. 1996; Vityk & Bodnar 1998; associated with galena (Lattanzi et al. 1989), but
Bodnar 2003b). In orogenic deposits, these co- no visible or microscopic gold was found associated
genetic groups would be trails or clusters of inclu- with the groups of fluid inclusions we studied.
sions paragenetically coeval with Au-precipitation The 17 FIAs (Goldstein & Reynolds 1994;
events. We stress that the quest for univocal petro- Bodnar 2003a) we studied (Table 3) were screened
graphic evidence for ore fluid entrapment during from c. 100 polished blocks of quartz veins. They
gold deposition is not an easy exercise and the have been selected based on two fundamental cri-
number of clearly useful assemblages is limited. teria. The first is the field and petrographic evidence
Table 2. Characteristics of samples used in this study
Deposit Sample name Characteristics
Berezovskoye* Cryst Large euhedral crystal (c. 8 cm in length) from a cavity in Au-bearing
carbonate-quartz vein hosted by plagiogranite porphyry
Berezovskoye* 3 Gold-bearing, ladder quartz-carbonate-sulphide vein hosted by
plagiogranite porphyry
Pestarena† 21C Au-bearing, quartz-pyrite-carbonate vein (3 cm-thick) crosscutting
muscovite schists
†
Pestarena 22A Au-bearing, quartz-carbonate vein with euhedral (1 cm long) quartz
prisms. Vuggy texture
Red Hill/Kanowna‡ RH3 Collected at decline of Red Hill mine, 50 m from entrance. Very clear
well-developed quartz crystal from vein margin. Vuggy vein cutting
dacitic porphyry, which is hydrothermally altered by quartz, albite,
muscovite, carbonate and pyrite
Sigma Audet Barren, shear-hosted quartz-tourmaline-pyrite-chalcopyrite vein
outcropping on a surface outcrop 5 km E of the Sigma deposit. Vein
emplaced at contact between crudely stratified pyroclastic rocks and
feldspar porphyry dykes. It crosscuts a foliated sequence of tilted
pillowed andesite
Sigma 1138 drift Subhorizontal, Au-bearing quartz-tourmaline-carbonate vein
crosscutting andesite. Depth: 415 m
Sigma 2321W stope Subhorizontal, Au-bearing quartz-tourmaline-biotite vein crosscutting
feldspar porphyry. Depth: 913 m
Sigma 2502 WA Subhorizontal, Au-bearing quartz-tourmaline-calcite-pyrite vein
stope 10 crosscutting porphyrytic diorite. Quartz ribbons alternate with
tourmaline-calcite levels or well preserved tourmaline rosettes.
Euhedral quartz crystals attached also to the vein walls. Depth: 974 m
Sigma DDH 16280 South plunging exploratory diamond drill hole within the Lamaque
deposit intersecting a 80 centimetre-thick, subvertical, Au-bearing
quartz-tourmaline vein. Depth: 1692 m
Wattle Gully‡ SG1 Level 5 of Wattle Gully deposit. Clear, well-developed quartz crystal
(c. 1 cm diametre) from Au-bearing quartz vein hosted by black
carbonaceous shales and slates
*Samples provided by V. Yu. Prokof’ev (Russian Academy of Science).

†
Samples provided by P. F. Lattanzi (University of Cagliari, Italy).
‡
Samples provided by E. de Clarke Earth Sciences Museum, University of Western Australia (Ho’s collection).
for the lowest level of strain in the vein samples, and Microthermometry
the second is the closest possible paragenetic rela-
tionship with Au. Five FIAs spatially associated Microthermometric measurements were carried
with Au were documented in samples 1138 drift out in part at the Institute of Geochemistry and
and DDH 16280–1 from the Sigma deposit (Fig. Petrology of the ETH of Zurich using a Linkam
1). They are hosted, together with thin tourmaline THMSG 600 heating/freezing stage attached to
rosettes, by optically undeformed quartz (Fig. 1a, b) a Leitz Orthoplan petrographic microscope, and
or occur as secondary trails subparallel to Au-filled in part at the Department of Earth and Environ-
microfractures (Fig. 1c, d). These assemblages iden- mental Sciences of the University of Bologna using
tify two specific stages of Au deposition, which were a Linkam THMSG 600 heating/freezing stage
most probably preceded and followed by other mounted on an Olympus BX51 petrographic micro-
Au precipitation stages. Textural analysis carried scope. The stages were calibrated using known
out at the outcrop (Garofalo 2004a) and microscopic phase transitions in synthetic fluid inclusions (H2O
scales (Fig. 1c) suggest that Au precipitation events and H2O-CO2 fluids), which allows precise deter-
within orogenic deposits are most probably uncoun- minations between at least 257 8C and 375 8C.
table. Thus, the ore fluid properties we determine Considering read-out precision, the measured tem-
here do not necessarily constrain the entire spectrum peratures have a precision of c. 0.5 8C for mea-
of all Au precipitation conditions in the five deposits. surements at T , 0 8C and 1 8C for measurements
Below we show that this is only an apparent limit- at T . 200 8C. Reproducibility has been determined
ation to our study. with duplicate or triplicate measurements of
Table 3. Characteristics of the studied fluid inclusion assemblages
Deposit Sample No. of No. Fluid Paragenetic relations

FIAs inclusions
in FIAs
Berezovskoye Cryst 1 52 No apparent relations with Au deposition

Berezovskoye 3 1 31 No apparent relations with Au deposition
Pestarena 21C 1 24 Primary FIA from a quartz enclave within pyrite
crystal attached to vein wall. No apparent
relations with Au deposition, but Au in this
sample reported in previous study of deposit*
Pestarena 22A 2 48, 35 Primary groups of FIAs at core and rim of euhedral
quartz crystal. No apparent relations with Au
deposition, but Au in this sample reported in
previous study of deposit
Red Hill/ RH3 1 31 L- and V-rich inclusions along growth band in
Kanowna undeformed quartz. No textural relations with Au
deposition
Sigma Audet 1 68 Cluster of inclusions within vein quartz and no
apparent relations with Au deposition, but also no
detectable Au in bulk vein (St. Croix, pers. com.)
Sigma 1138 drift 2 25, 83 Primary FIAs within vein quartz at progressive
distance from a group of Au nuggets
Sigma 2321W stope 3 69, 26, 31 Pseudosecondary FIAs cutting partially host quartz
and tourmaline set in biotite-chlorite groundmass.
No apparent relations with Au deposition, but
visible Au documented in same vein
Sigma 2502 WA 1 65 Primary FIA within quartz ribbon in crack-seal vein
stope 10 with tourmaline and carbonate. No apparent
relations with Au deposition, but visible Au
documented in same vein
Sigma DDH 16280 3 32, 74, 69 Secondary trails of inclusions within vein quartz, all
subparallel to a Au-filled microfracture
Wattle Gully SG1 1 63 Primary FIA made of cluster of fluid inclusions
within undeformed vein quartz. Inclusions have
variable phase proportions within FIA. No
textural relations with Au deposition, but visible
Au documented in the vein
*, Lattanzi et al. (1989).
individual inclusions and is 0.1 8C at low tempera- transitions were measured using the cycling method
tures. Because decrepitation plagued many high-T described by Goldstein & Reynolds (1994), and care
measurements, reproducibility of the total hom- was taken in recording the minimum and maxi-
ogenization temperatures, T h(total), was not poss- mum values for each assemblage. Table 4 summar-
ible to determine. izes the microthermometric determinations made
All low-temperature phase transitions have been on the 17 FIAs.
measured using a standard procedure. Samples were
first rapidly cooled to c. 2180 8C in order to detect Raman spectroscopy
the possible formation of vapour, clathrate, ice, salt-
hydrates and carbonic solid phase in place of carbo- Raman microprobe analyses were carried out at
nic and aqueous liquids. On progressive heating the Department of Physics and Earth Sciences
(rate ¼ 223 8C/min), up to five phase transitions of the University of Parma (Italy) using a Jobin-
were observed in the inclusions, namely melting of Yvon Horiba LabRam spectrometer equipped with
the carbonic phase, Tm(CO2); melting of the ice, He –Ne laser (emission line 632.8 nm) and motor-
Tm(ice); melting of the clathrate, Tm(clat); and ized XY stage. The spectral resolution is nearly
homogenization of the carbonic phase, T h(CO2). 2 cm21. The confocal hole has been adjusted in
After completion of laser-Raman and LA-ICP-MS order to obtain a spatial (lateral and depth) resol-
analyses, the T h(total) for the remaining inclu- ution of 1–2 mm. Most of the spectra were obtained
sions in the FIAs were determined. All the phase using a 50× objective (N.A. 0.75), although for
Fig. 1. Microstructural criteria used to relate the entrapment of the orogenic fluid inclusions with Au deposition.
(a, b) Photomicrograph and outline showing the open-space filling texture of an Au-bearing vein (sample: Sigma
1138 drift). Occurrence of FIA 1 within undeformed quartz associated with tourmaline, calcite and Au suggests that in
this vein fluid entrapment was coeval with mineral precipitation. Note the variable phase ratios of the inclusions making
the assemblage. (c, d) Outline and photomicrograph of trails of fluid inclusions and Au-filled microfractures cutting vein
quartz and adjacent to a pyrite-pyrrhotite-sphalerite-chalcopyrite aggregate (sample: Sigma DDH 16280). Note the grey
tone on the left marks an area of evident quartz re-crystallization. The parallel strike of fluid inclusion trails and Au
microfracture suggest that fluid inclusion entrapment accompanied nearby gold precipitation. Note the entrapment of
one assemblage (FIA 6) within newly formed quartz.
shallow inclusions also a 100× objective (N.A. between 1100 cm21 and 1800 cm21 for the study
0.90) was used. The calibration was made using of CO2 spectra, and between 2500 cm21 and
the 520.7 cm21 Raman line of silicon. A wide spec- 3300 cm21 for CH4 and H2S. The acquisition time
tral range (100– 3600 cm21) was scanned for each for each spectral window was 120–240 s, with two
inclusion for the presence of CO2, N2, CH4 and accumulations. The power on the sample surface
H2S, but the final acquisitions were made mainly is nearly 1 mW but the power on the analysed
80
Table 4. Summary of microthermometric data*

Sample FIA n Depth Range Phase state Tm Tm Tm Th CO2 hom. Bulk T h(tot) Th mass%
No. (m) of wvap at Tlab (CO2) (Ice) (Cla) (CO2) mode† XCO2 mode (total) NaCleq
Ber. Cryst 1 52 462 28.1– 56.5 Laq –Vcar 2 57.4 + 0.1 2 12/26.5 5.0 –7.3 (L) 7.0 –31.0 L, C 0.091 (L)‡ L and V 202– 266 (L) 4.70 (L)‡
Laq – Lcar – Vcar 5.0– 9.2 (V) 0.140 (V)‡ 203–246 (V) 0.90 (V)‡
Ber. 3 1 31 262 19.8– 50 Laq –Lcar; 2 57.5 + 0.1 2 7.5 (aver) 8.6 + 0.9 19.8 –30.2 L, C 0.133 (L)‡ L and V 249– 265 (L) 3.13 (L)‡
Laq – Lcar – Vcar (n ¼ 2) 0.246 (V)‡ 250–295 (V) 0.39 (V)‡
Pest 21C 1 24 n.a. 5– 45 Laq –Vcar 2 57.0 + 0.0 7.3 + 0.8 n.a. L and V 303– 312 (L) n.a.
296–331 (V)
Pest 22A 1 (core) 48 n.a. 17.4– 35 Laq –Lcar; 2 58.2 + 0.4 2 9.9 + 0.4 7.4 + 0.3 6.5 –29.0 L 0.034 (L)‡ L and V 193– 305 (L) 5.39 (L)‡
Laq – Lcar – Vcar n.a. (V)‡ 207–275 (V) n.a. (V)‡
Pest 22A 2 (tip) 35 n.a. 18.1– 30 Laq –Lcar; 2 58.0 + 0.1 2 8.2 + 0.2 7.9 + 0.4 2 14.0 –27.5 L, V, C 0.046 (L)‡ L and V 187– 290 (L) 3.85 (L)‡
Laq – Lcar – Vcar 0.076 (V)‡ 210 (V) 3.48 (V)‡
RHK RH3 1 36 n.a. 5– 35 Laq – L– Vcar 2 56.1 + 0.1 8.9 + 0.2 23.6 –31.4 L, C 0.030 (L)‡ L and V 255– 307 (L) 1.48 (L)‡
0.094 (V)‡ 262–302 (V) 1.73 (V)‡
Sigma Audet 1 68 0 5– 50§ Laq –Vcar; 2 56.8 + 0.6 2 12/216 6.4 + 0.5 2 4.5 –30.9 L, C 0.061 (L) L and V 172– 354 (L) 5.56 (L)
Laq – Lcar – Vcar 0.168 (V) 226–362 (V) 4.14 (V)
P. S. GAROFALO ET AL.
Sigma 1138 drift 1 25 411 5– 50 Laq –Vcar; 2 56.9 + 0.1 6.7 + 1.3 9.2 –29.1 L 0.06 (L)‡ n.a. 6.5 (L)

Laq – Lcar – Vcar 0.14 (V)‡ 4.3 (V)
Sigma 1138 drift 2 88 350 5– .50 Laq –Vcar; 2 56.8 + 1.0 2 7.3 + 0.7 6.2 + 0.2 2 4.1 –30.5 L, C 0.036 (L)‡ L and V 198– 370 (L) 6.07 (L) ‡
Laq – Lcar – Vcar n.a. (V)‡ 235 (V) n.a. (V)‡
Sigma 2321W 2 69 913 5– .50 Laq –Vaq 2 0.2/24.0 3.8 and 7.4 L and V 301– 412 (L) 2.74 (L)}
(n ¼ 2) 374–404 (V) 0.35 (V)}
Sigma 2321W 3 26 913 5– 50 Laq –Vaq 2 0.2/22.1 L 314 + 39 1.7 + 1.2}
Sigma 2321W 4 31 913 5– .50 Laq –Vaq 2 0.2 23.5 L and V 241– 420 (L) 1.05 (L)}
372–418 (V) 0.35 (V)}
Sigma 2502W 5 65 974 10– .50§ Laq –Vcar; 2 56.7 + 0.1 2 6/211 7.5 + 0.3 2 12.1 –30.3 L, V, C 0.034 (L) L and V 177– 335 (L) 3.41 (L)‡
Laq – Lcar – Vcar 0.095 (V) 193–377 (V) 4.37 (V)‡
Sigma DDH 16280 6 32 1692 10– .50 Laq –Vaq 0.0/22.0 L and V 281– 393 (L) 1.2 (L)}
359–377 (V) 1.3 (V)}
Sigma DDH 16280 7 74 1692 10– .50 Laq –Vaq 2 0.6/ –4.0 L and V 239– 423 (L) 3.0 (L)}
345–410 (V) 1.1 (V)}
Sigma DDH 16280 8 69 1692 20– .50 Laq –Vaq 2 0.6/ –4.2 L and V 297– 397 (L) 1.7 (L)}
331–393 (V) 1.1 (V)}
Wattle Gully SG1 1 63 c. 50 12.5 Laq –Vcar 2 56.7 (n ¼ 3) 2 2.2 + 0.2 7.1 + 0.3 0.031 L 197 + 3 4.7 + 0.31
*All T are in 8C. Data report the ranges of measured properties of fluid inclusions within individual assemblages. Symbols L and V in the column ‘T h (total)’ denote the temperature ranges of inclusions homogenizing by bubble disappearance (L)
or by liquid disappearance (V) within the same assemblage. The columns ‘Bulk XCO2’ and ‘mass% NaCleq’ report the calculated molar fractions of CO2 and the equivalent salinities of the low-T h(total) inclusions homogenizing via bubble
disappearance (L) and liquid disappearance (V).
†
Modes of homogenization of the carbonic phase: L-bubble-point transition; V-dew-point transition; C-critical transition.
‡
Calculated using the equations of state of Duan et al. (1992a, b) and Duschek et al. (1990)) within program Q2 of Bakker (1997, v. 12/02). Calculations do not consider presence of CH4 in the gas phase and additional solutes other than NaCl
§
Refers to the quantities Vcar + Lcar

Estimated from the L/V ratios correspondent to L- and V-rich inclusions.
}
Calculated using equation 1 of Bodnar (1993).
1
Calculated using the equations of state of Duan et al. (1992a, b) within program ICE of Bakker (1997, v. 12/02).
n.a: not available.
inclusions has to be considered lower due to reflec-

tions and scattering.
Analyses were carried out mostly on homo-
geneous vapour bubbles. Representative inclusions
were selected among the following FIAs: Berezovs-
koye Cryst and 3, Pestarena 22A-FIAs 1 and 2,
Sigma 1138-FIA 2, Sigma 2321W-FIA 2, Sigma
2502 W, Sigma 16280-FIA 7 and Wattle Gully
SG1. Carbon dioxide densities in individual inclu-
sions were calculated using the separation between
the two Raman bands of CO2 (1388 cm21 and
1285 cm21) using the method shown by Kawakami
et al. (2003), while the CO2 molar fractions were
determined with the method of Burke (2001). The
instrumental efficiency for CO2 was set to 0.92 in
all calculations. Results are provided in Table 4.
Spindle stage determinations

We used the method of Bakker & Diamond (2006)
to measure the volume fraction of the vapour
phase (wvap, i.e. vapour/liquid or degree of filling)
in representative inclusions from the FIAs of sam-
ples Berezovskoye Cryst, Berezovskoye 3, Pestar-
ena 22A (FIA 1 and 2), Sigma 1138 (FIA 2) and
Wattle Gully SG1. We slightly modified the
approach of Bakker & Diamond (2006) because only
the assemblage Wattle Gully SG1 contained inclu-
sions with a consistent degree of filling (Table 4).
In the heterogeneous assemblages, we combined
microthermometric determinations (Tm(clat) and
T h(CO2)) with petrographic constraints to identify
end-member inclusions with the smallest wvap and
the highest bulk salinity, and the inclusions and
the largest wvap and the lowest bulk salinity. These
inclusions proved to be among those with the
lowest T h(total), showing that this method was
quite efficient in identifying inclusions representa- Fig. 2. Estimation of the volume fraction of a regularly
tive of both sides of the solvus. An example wvap cal- shaped, V-rich fluid inclusion from a heterogeneous fluid
culation is reported in Figure 2 for a vapour-rich assemblage. This inclusion had microthermometric
inclusion belonging to FIA Berezovskoye 3. Data properties that corresponded to the lowest salinity of the
host assemblage. (a) Photomicrograph showing the
show that the maximum projected area of this petrographic features of this inclusion, for which a
inclusion lies at a rotation angle of 2258 (Fig. 2b, degree of filling of c. 40% is visually estimated. (b)
see arrow). This angle, when intersected by the area- Projected area of the inclusion v. angle of rotation in the
fraction curve (Fig. 2c), corresponds to an area frac- spindle stage. (c) area fraction of the vapour phase
tion of the vapour phase of 56.6%, which most v. angle of rotation in the spindle stage.
closely approximates the degree of filling of the
inclusion (Bakker & Diamond 2006). All the wvap
determined by spindle stage measurements are Zurich. Analyses were conducted on two UV ArF
reported in Table 4. (193 nm) excimer lasers (GeoLasQ and GeoLasC,
Lambda Physik, Göttingen, Germany) coupled
Laser Ablation ICP-Mass spectrometry with a quadrupole ICP-MS (ELAN 6100DRC+,
Perkin-Elmer, Waltham, Massachusetts) and micro-
LA-ICP-MS analyses were conducted on 133 indi- scope optics to monitor analysis. The laser repeti-
vidual inclusions representative of 14 FIAs from tion rate was set equal to 10 Hz on both systems,
ten samples. Analyses were carried out at the Insti- with different beam fluence in the GeoLasQ
tute of Geochemistry and Petrology and at the (9, 15 Jcm22) and GeoLasC (3 Jcm22) systems.
Laboratory of Inorganic Chemistry of the ETH Samples were loaded within an in-house-built
ablation cell (50 cm3) and analyses were performed We determined analyte concentrations by con-
by single-hole straight ablations. The mass spectro- sidering only analyses with signal intensities above
meter conditions were tuned daily for high sensitiv- background and by grouping together inclusions
ity and low oxide ratio as follows: ICP rf power, with the same signal structure (symmetric/asym-
1380 W; nebulizer flow ¼ 0.8 L min21; He gas metric, see discussion below), which proved impor-
flow ¼ 1.0 L min21; Ar auxiliary gas flow ¼ 0.75 tant for Au determinations. Results are reported in
L min21; plasma gas, 17.5 L min21; and ThO+/ Table 5, which lists also our measured ranges of
Th+ ,0.5%. Mg (1–2000 mg/g) and Mn (10 –300 mg/g) in
The silicate glass SRM NIST610 was used as samples M2 and 3 from Berezovskoye and WG
external reference material to quantify signal inten- SG1 from Wattle Gully. These assemblages were
sities and correct for instrumental drift. Quanti- the only ones in which we detected Mg and Mn;
tative determinations of element concentrations hence, we do not consider Mg and Mn sufficiently
were calculated with a spreadsheet program using characterized.
the method described by Heinrich et al. (2003). The development of parallel transient signals in
Additional details on analytical methodology and LA-ICP-MS analysis are typically considered evi-
application of LA-ICP-MS for analysis of single dence for liberation of the inclusion fluid during
fluid inclusions have been reported by Günther ablation (e.g. Heinrich et al. 2003); therefore, we
et al. (1998), and further details on the measure- consider the systematic correlation between the
197
ment of Au in fluid inclusions can be found in Au and 23Na signals (Fig. 3) as evidence for Au
Ulrich et al. (1999). Inclusions were scanned to being a fluid inclusion component. We calculated
detect a large number of elements using various Au concentrations using the 23Na and 197Au sig-
selections of the following list of isotopes: 7Li, nal intensities, but considering their distinct sig-
11
B, 23Na, 24Mg, 25Mg, 26Mg, 27Al, 28Si, 29Si, 37Cl, nal shapes. 197Au and 23Na count-rate traces were
39
K, 47Ti, 49Ti, 51V, 53Cr, 55Mn, 56Fe, 57Fe, 63Cu, either both strongly asymmetric (e.g. inclusion 1
65
Cu, 66Zn, 68Zn, 75As, 85Rb, 88Sr, 89Y, 93Nb, of Fig. 3) or were both symmetric (e.g. inclusions
120
Sn, 121Sb, 123Sb, 133Cs, 137Ba, 138Ba, 197Au, 2, 4 and 5 of Fig. 3). Similar asymmetric/symmetric
205
Tl, 206Pb, 207Pb, 208Pb, 209Bi, 232Th and 238U, signals were also observed for 11B. Asymmetric
but quantification was possible only for Na, K, B, and symmetric signals occurred during ablation of
Cu, Li, Sr, Mn, Mg, As, Rb, Ba, Cs, Sb and Au in inclusions with the same petrographic features
133 inclusions. The estimated limits of detection (i.e. shape, dimension and proportion of volatile
for these elements show the following ranges (all content) using the same acquisition parameters;
in mg/g): Na ¼ 3 –5000; K ¼ 3– 9000; B ¼ 15– therefore, they did not depend on instrument set-
14000; Cu ¼ 1– 2300; Li ¼ 5–3000; Sr ¼ 0.1– tings or inclusion dimensions. We explain the occur-
200; Rb ¼ 0.2 –300; Ba ¼ 7– 700; As ¼ 0.3 –100; rence of asymmetric signals by the possible action
Cs ¼ 0.7–100; Sb ¼ 0.4–400; and Au ¼ 0.04–400. of two concurrent processes: one is the abrasive
In this type of analyses, limits of detection (which wearing generated by the polishing of the host
are directly proportional to the ablation yield) quartz, and the other is the explosive breaching
depend most dominantly on the volume of liquid of shallow FIs at the start of ablation. Abrasive
within the inclusions and secondly on the ionization wearing forms during the polishing process, consists
potential of the elements. The ablated volumes of of the formation on the sample surface of an amor-
liquid are on the order of a few tens of mm3 at the phous thin film (,200 nm) made of a mixture of
most. A limitation to element quantification is given sample material and contaminants (Kim et al.
in general by isobaric interferences potentially gen- 2002; Rémond et al. 2002), and is considered an
erated by the presence of polyatomic species of important source of contamination in fluid inclusion
plasma gas ions. In the used element menu, the analysis (Pettke et al. 2012, and refs therein). The
most important of these interferences is given by major implication of such wearing would be the
40
Ar35Cl+, which potentially interferes with the detection of spurious analyte signals during host
mono-isotopic 75As and makes As determinations mineral ablation. In our quartz samples, we note
difficult (May & Wiedmeyer 1998). In our fluid that where ablation was carried out away from
inclusions, the range of Cl concentrations is low fluid inclusions, no spurious Au or B signals were
due to the low bulk salinity of the entrapped fluid detected (e.g. Fig. 3b); hence, we exclude the pos-
(see below), and no correlation exists between the sibility that abrasive wearing caused significant
calculated Na and As concentrations. As a conse- contamination from the smear of Au and a B-
quence, we consider the contribution of the 40Ar bearing phase on the samples. We therefore explain
35Cl+ interferences to be very low in our samples. the formation of asymmetric Au, Na and B signals
However, because we did not introduce any correc- with the ablation of shallow inclusions located
tions to the calculated As concentrations, we prefer close to the amorphous layers generated by abrasive
reporting As values as information values. wearing. These inclusions experienced explosive
Table 5. Concentration of fluid components in the FIAs*
Sample FIA # No. of Na K B Au As Sr Ba Rb Cu Mg Li Cs Mn Sb Pb

analyses (wt%) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g) (mg/g)
AU-TRANSPORTING HYDROTHERMAL FLUIDS

Berez. M2 1 13 1.2 + 0.0 2531 + 1131 427 + 220 ,LOD 28 + 9 10 + 9 14 + 9 2292 62, 61 10– 322 ,LOD
(n ¼ 1) (n ¼ 2) (n ¼ 6)
Berez. 3 1 18 0.6 + 0.0 1330 + 667 444 + 240 ,LOD 417 + 296 18 + 13 15 (n ¼ 1) ,LOD 133 1– 2060 99, 54 5+2 ,LOD 3 (n ¼ 1)
(n ¼ 1) (n ¼ 4) (n ¼ 2)
Pestar. 22A 2 (tip) 4 0.7 + 0.1 3681 + 2747 ,LOD 142, 124 19, 22 ,LOD 17 + 6 122 ,LOD ,LOD

(n ¼ 2) (n ¼ 2) (n ¼ 1)
RHK RH3 1 1 0.18 ,LOD ,LOD 201 ,LOD 1 51 29 ,LOD 15
Sigma Audet 1 15 2.6 + 0.2 709, 768 1422 + 537 ,LOD 107, 207 5, 50 8 (n ¼ 1) 350
(n ¼ 2) (n ¼ 2) (n ¼ 2) (n ¼ 1)
Sigma 1138 1 5 1.0 + 0.8 ,LOD 129, 234 ,LOD 79 (n ¼ 1) ,LOD ,LOD ,LOD ,LOD
drift (n ¼ 2)
Sigma 1138 2 7 0.1 + 0.1 ,LOD 514, 731 ,LOD 9, 18 (n ¼ 2) ,LOD ,LOD ,LOD ,LOD ,LOD
drift (n ¼ 2)
Sigma 2321W 2 13 1.1 + 0.6 ,LOD 359 + 163 2 –5 52 (n ¼ 1) 252 (n ¼ 1) 461 (n ¼ 1)
(n ¼ 3)
Sigma 2321W 4 4 0.4 + 0.3 ,LOD 1.4 + 1
Sigma 5 15 1.7 + 0.2 4816 + 5047 134 + 53 3+2
2502WA
Sigma DH 6 10 0.6 + 0.0 852, 1284 3 (n ¼ 1)
16280 (n ¼ 2)
Sigma DH 7 9 1.1 + 0.4 ,LOD L: ,LOD
16280
Sigma DH 8 6 0.7 + 0.4 ,LOD 916 (n ¼ 1)
16280
WG SG1 1 7 0.4 + 0.2 621 + 323 218 + 175 ,LOD 31 + 12 17 + 5 2, 2 (n ¼ 2) ,LOD 20 (n ¼ 1) 13 (n ¼ 1) 6+2 2, 6
(n ¼ 2)
*Rows report calculated average concentrations of analytes from at least three fluid inclusions and their correspondent 1s variation within the assemblage. Fewer determinations are listed individually. Only the Au concentrations of ‘sym-
metrical’ inclusions (Fig. 3) are reported. Symbol ,LOD indicates concentrations below the calculated limit of detection. Blank entries indicate no measurements.
83
(a) DH 16280
107 FIA 7
start of ablation
106 next pit
105 background
asymmetrical Si
104 symmetrical Na
B 3σback. 103
2 B
Au 3σback.10
10 Au
1 2 3 4
10 20 30 40 50 60 70 80 90
(b) DH 16280
107 FIA 6
counts per seconds
106
105
104
103
102
10
5 6
1
10 20 30 40 50 60 70 80 90
(c) 2502 WA
107
106
105
104
103
102
10
7 8
1
30 40 50 60 70 80 90 100
Seconds
Fig. 3. Transient LA-ICP-MS signals of eight Au-bearing fluid inclusions from different assemblages. Note the
asymmetric (FI 1 and 3) and symmetric (FI 2, 4 and 5) 197Au signals.
opening simultaneously with the breaching of the variable LODs for inclusions belonging to the
amorphous layers (Fig. 3a), while deep inclusions same FIA (Longerich et al. 1996; Heinrich et al.
experienced regular opening and generated sym- 2003). To show how LODs and Au concentrations
metrical signals. depend on the factors listed above, we highlighted
For Au and B determination, particular attention in Figure 3 the 3sbackground of the 197Au and 23Na
was paid in the evaluation of their limit of detection signals (coloured dotted lines). According to Long-
(LOD) in each analysis. Because in LA-ICP-MS erich et al. (1996) and the data reduction software
analyses signal intensity is a function of inclusion procedure (Jackson 2005), the 3sbackground of an
size, time of sampling, acquisition speed, number analyte is related to the LOD by the expres-
of isotopes measured, background counts and stan- sion: LOD ¼ (3sbackground/(S × Y)) . ((1/nb) + (1/
dard deviation of the background, we obtained na))1/2, where S is the interpolated sensitivity, Y is
the ablation yield of the internal standard relative to

the reference material, nb is the number of time symmetrical liquid-rich
slices in the ablation time interval for the back-
ground; and na is the number of time slices in the symmetrical vapour-rich
ablation time interval for the analyte. This
asymmetrical liquid-rich
expression indicates that inclusions with well-
structured 197Au signals significantly above the asymmetrical vapour-rich
3sbackground have concentrations above the LOD
(e.g. inclusion 4 in Fig. 3), while inclusions having 800
signals only slightly above the 3sbackground intensity
(e.g. inclusion 6) or with poorly structured signals
(e.g. inclusion 8) have concentrations below the 600
Au counts
LOD. Similarly, relatively small inclusions ana-
lysed for a short time but with a structured signal 400
(e.g. inclusions 2, 3 and 5) will result in Au concen-
trations below the LODs. This definition of LOD range of Au concentration:
implies that poorly defined 197Au signals might 200 0.5 - 5 µg/g
lead to ‘false negative detections’ (i.e. to cases in
which no Au is detected although something is
0
present; cf. Tanner & Günther 2009; Pettke et al. 0 20 40 60 80
2012). Approaches that tend to assign a concen- 3
tration to these false negative detections consider Na 10 counts
the ‘minimum detectable values’ of short transient Fig. 4. Correlation between Na and Au total counts from
signals – LD, which are detection limits based on 45 LA-ICP-MS analyses. Counts have been calculated
Poisson distribution statistics. These limits relax using the ICP-MS counting statistics of each fluid
the statistical significance threshold of 3sbackground inclusion. The full symbols named ‘symmetrical’ (either
and estimate concentrations using an algorithm liquid- or vapour-rich) correspond to regular ablation
based on background and analyte count rates, the signals. They show a positive Na-Au correlation,
number of sweeps for background and analyte inte- indicating that the two analytes were in solution within
gration sections, and dwell time used for recording the inclusion fluid. The reported range of Au
concentrations in these inclusions is considered
elements (e.g. Pettke et al. 2012, for a discussion).
representative of the ore fluid.
A detailed discussion on the benefits obtained by
the use of this alternative approach for Au determi-
nations is not the object of the present work. each other (Fig. 4; 23Na and 11B correlation not
However, we note that LODs determined with the shown), while inclusions having an asymmetric
equation reported above and LDs obtained from structure show poor correlations. This shows that
Poisson statistics analysis are very close to each only analysis of vapour- and liquid-rich inclusions
other (within 20% or less), especially for analyses with a symmetrical signal shape lead to meaningful
in which a low number of sweeps of 197Au is gath- Au determinations. Among the 45 Au analyses of
ered (Pettke et al. 2012, cf. Fig. 4). Therefore, the this study, only 31 resulted to be symmetrically
use of alternative approaches to LOD calculations shaped and correspond to a concentration range of
would not change significantly the results of our 0.5 –5 mg/g. This is interpreted as the true range
determinations. of Au concentrations in the Sigma ore fluid. We
We determined Au and B concentrations in the stress that a 0.5–5 mg/g concentration does not cor-
assemblages by using only inclusions in which the respond to a measure of Au solubility at the labora-
total number of counts of 23Na, 197Au and 11B are tory temperature and pressure. At those conditions,
truly correlated with each other. To show this corre- and for the S concentration estimated for the
lation, we calculated Ci = Ri · ti · (tdwell /tsweep ) for inclusion fluid (see below), the predicted range of
these elements in each individual analysis. Note Au concentrations is on the order of a few ng/g
that in this relation Ci is the number of total (cf. Pokrovski et al. 2014).
counts recorded for analyte i during an individual
analysis (which is distinct from the count rates – Fluid mineral equilibria
cps), Ri is the background corrected count rate for
analyte i, ti is the total integration time of analyte Equilibrium and speciation calculations have been
i, tdwell is the dwell time of that analyte i and tsweep carried out with the CSIRO-SGTE THERMO-
is the sweep time. Results show that only inclu- DATA 5.2 software package (Turnbull & Wadsley
sions having symmetrical 23Na, 197Au and 11B signal 1986; updated by Pokrovskii Liu and Heinrich,
structures have total counts linearly correlated with unpublished data). This software includes HKF
parameters and properties of minerals and aqueous Eleven assemblages hosted the aqueous-carbonic
species (Johnson et al. 1992), and the thermodyn- fluid, while six assemblages from two samples of
amic data for minerals from the THERMOCALC the Sigma-Lamaque deposit (2321W stope and
database of Holland & Powell (1990) as amended DDH 16280, Table 2) hosted the aqueous fluid.
by Sverjensky et al. (1991). We carried out the cal- The phase ratios of inclusions making individual
culations using the revised internally consistent assemblages were mostly variable at room tempera-
set of HKF-equation-of-state parameters for Au(I) ture (Fig. 1). This suggests that the ore fluid was in
aqueous complexes of Pokrovski et al. (2014). a heterogeneous state at the time of entrapment.
These recently derived parameters reproduce the
experimental solubility constants of the reactions Microthermometry
(Stefansson & Seward 2004):
The microthermometric data of the entire sample
Au(s) + H2 S(aq) = AuHS(aq) + 0.5 H2 (g), (1) set show that the bulk properties of the ore fluids
are quite uniform across the deposits. With the
and exception of the Pestarena samples, melting of
the carbonic phase took place between 256 8C
Au(s) + H2 S(aq) + HS− (aq) = Au(HS)−2 (aq) and 257 8C in the sample set (Fig. 5c, g, k, o),
+ 0.5 H2 (g) (2) showing that CO2 is the dominant species of the
vapour phase of the aqueous-carbonic fluid, and in
within 0.3 and 0.6 log units at 200– 500 8C and the presence of only modest proportions of other
50 MPa, respectively. They reproduce also the gases (mainly CH4, see the Raman spectrometry
solubility constants of reactions (1) and (2) as deter- section below).
mined by Tagirov et al. (2005) at 350 8C and Measurements of Tm(clat), carried out almost
200 MPa within 0.4 log units. exclusively in the presence of vapour, carbonic
Parameters for the B aqueous species B(OH)2 4 liquid and aqueous liquid, cluster between 7 8C
and NaB(OH)4 were taken from Pokrovski et al. and 9 8C, the only exeption being the Berezovskoye
(1995) and used in addition to those available in samples (Fig. 5a, d, h, l, p). Interestingly, there is
THERMODATA (B(OH)3, BO2 2 ). These data have no significant difference between the Tm(clat) of
been used in conjunction with standard thermo- vapour- and liquid-rich inclusions in individual
dynamic properties of tourmaline end members assemblages. The carbonic phase of most assem-
(Garofalo et al. 2000) to predict the concentration blages homogenizes into the liquid phase or by criti-
of B-bearing aqueous species in the ore fluid. cal homogenization. Very few dew point transitions
were observed, and the distribution of T h(CO2)
is very broad from ,0 8C to 31.4 8C (Fig. 5e, i,
Results m, q). Also for this phase transition, there is little
difference between liquid- and vapour-rich inclu-
Fluid types sions. The resulting range of calculated bulk sali-
nities for the aqueous-carbonic fluid is 0.3–5.4
Among the analysed FIAs, three compositional mass% NaCleq, with little difference between
types were recognized at room temperature: liquid- and vapour-rich inclusions.
(1) Aqueous. Two-phase fluid represented by an A relevant feature of the microthermometric
aqueous liquid and a water-rich vapour show- database is the relative consistency of fluid inclu-
ing both constant and variable phase pro- sion properties at the scale of individual vein
portions within single FIAs (Fig. 1c, d); quartz crystals. This is shown by the close similarity
(2) Aqueous-carbonic. Two- to three-phase fluid between the data of two FIAs from sample Pestarena
made of a carbonic liquid, a carbonic-rich 22A (Fig. 5). These assemblages are of primary
vapour and an aqueous liquid. This fluid type inclusions located at the core and tip, respectively,
has a high variability of phase proportions of a euhedral vein crystal (Table 2).
within individual assemblages (Fig. 1a, b). Ice melting in the aqueous FIAs has been com-
(3) Two-phase CO2-rich inclusions associated monly difficult to observe. Bracketing of Tm(ice)
with the aqueous-carbonic inclusions and was possible, however, by observing the defor-
consisting of trails or clusters. This type of mation of the vapour bubbles observed during cycl-
inclusions corresponds to the high-density ing, and results show a temperature interval usually
CO2-dominated inclusions described above between 0 8C and 23 8C (Fig. 6). The calculated
and were not studied in detail because of the salinity of the aqueous fluid varied between 0.4
relatively good microthermometric database mass% and 2.7 mass% NaCleq(Table 4).
already available for this fluid type (cf. Pre- In the entire sample set, total homogeniza-
vious fluid inclusion studies section above). tion occurred between c. 200 8C and 420 8C (Fig.
(a) FIA 1
(b) 10
25 FIA 1
Frequency
20 8
Wattle Gully 15 6
SG1 10 4
5 2
0
3 4 5 6 7 8 9 10 150 200 250 300 350
(c) (d) (e) (f)
6 FIA 1 6 4 FIA 1
30 FIA 1 FIA 1
Frequency
4 4 2
Berezovskoye 2 2 Liquid Liquid
20 Liquid 0
M2 0 0 Vapor
10 2 Vapor 2 Vapor 2
0 4 4 4
-60 -59 -58 -57 -56 3 4 5 6 7 8 9 10 2 6 10 14 18 22 26 30 150 200 250 300 350
(g) (h) (i) (j)
16 16 FIA 2 6
50 FIA 2 12 FIA 2 FIA 2
Frequency
12
40 8 8
Red Hill 30 4 Liquid 4 Liquid 2 Liquid
RH3 20 4 Vapor 4 Vapor 2 Vapor
10 8
12 8
0 16 12 6
-60 -59 -58 -57 -56 3 4 5 6 7 8 9 10 2 6 10 14 18 22 26 30 150 200 250 300 350
(k) (l) (m) (n)
30 FIA 2 16 4 FIA 2 FIA 1
Frequency
25 tip 30 FIA 2 FIA 1 tip core

tip 12 core 2
Pestarena 20
20
FIA 2 Liquid
15 FIA 1 8 tip 0
22A 10 core FIA 1 Vapor
10 core 4 2
5
0 0 0 4
-60 -59 - 58 -57 -56 3 4 5 6 7 8 9 10 2 6 10 14 18 22 26 30 150 200 250 300 350
(o) (p) (q) (r)
50 FIA 5 20 FIA 5 8 FIA 5 FIA 5
Frequency
40 2 Liquid
Sigma 10
Liquid
4
Liquid 1
2502 WA stope 30
0 0 0
20 Vapor 1
(Au conc. > LOD) 10 10 4 Vapor Vapor
2
0 20 8
-60 -59 - 58 -57 -56 4 5 6 7 8 9 10 <0 2 6 10 14 18 22 26 30 150 200 250 300 350
Tm(CO2) \°C Tm(Cla) \°C Th(CO2) \°C Th(total) \°C
Fig. 5. Synoptic representation of a selection of microthermometric properties of the aqueous-carbonic FIAs. Each
row reports data from the same deposit, while data inspection along columns allow comparisons of the same phase
transition in different samples. Note that the division between liquid- and vapour-rich inclusions in the histograms is
based on the modality of total homogenization (bubble v. liquid disappearance), and not on the evaluation of
phase ratios.
5b, f, l, p, t and Fig. 6b, d, f ), although individual the Sigma inclusions are above 5, although mea-
assemblages record much narrower ranges (mostly surements range between 0.5 and 140, and CO2
300 –400 8C). With the only two exceptions docu- density is between 0.30 g cm23 and 1.02 g cm23.
mented at Sigma and Wattle Gully (FIAs ‘Sigma The CO2/CH4 molar ratio in the Pestarena inclu-
2321 W’ and ‘Wattle Gully SG1’, Table 4), total sions is always very high, the minimum being
homogenization in individual assemblages occurred equal to 38. Inclusions with this composition have
both via bubble disappearance (V L) and liquid a CO2 density of 0.72 g cm23, but those with a
disappearance (L V). The temperature ranges higher CO2/CH4 molar ratio have calculated CO2
at which these bubble- and dew-point inclusions densities as low as 0.53 g cm23. In the Berezovs-
homogenize is quite uniform across assemblages koye inclusions, the minimum CO2/CH4 molar
and between c. 200 8C and 350 8C. Table 4 reports ratio is equal to 161, and the corresponding CO2
the complete ranges of T h(total) recorded in the density is 0.96 g cm23. The calculated molar frac-
studied assemblages, but the values relative to tion of CO2 in the bulk aqueous-carbonic fluid
XCO2 and mass% NaCleq refer only to the low- (Table 4) ranges between 0.03 and 0.25 in the data
T h(total) inclusions of each assemblage. set. No detectable CO2 (but sometimes detect-
able CH4 and N2) characterize the aqueous fluid
Raman spectrometry inclusions of Sigma.
Data from Raman spectrometry confirm the micro- Laser Ablation-ICP-Mass Spectrometry
thermometric results whereby the vapour phase of
the aqueous-carbonic fluid is essentially domi- Fluid inclusion compositions show two fundamental
nated by CO2. Typical CO2/CH4 molar ratios in characteristics. First, all assemblages contain the
(a) (b)
3 FIA 6 3 FIA 6
Frequency
Sigma 2 2
DH 16280 1 Liquid 1
0 0
(Au conc. > LOD) 1 Vapor
1
2 2
3 3
-5.0 -4.0 -3.0 -2.0 -1.0 0.0 250 300 350 400
(c) (d)
20 FIA 7 4 FIA 7
Frequency
Sigma 10 2
DH 16280 Liquid
0 0
(Au conc. > LOD) Vapor
10 2
20 4
-5.0 -4.0 -3.0 -2.0 -1.0 0.0 250 300 350 400
(e) 20 (f)
FIA 8 4 FIA 8
Frequency
Sigma
10 Liquid 2
DH 16280 0 0
(Au conc. > LOD) Vapor
10 2
4
20
-5.0 -4.0 -3.0 -2.0 -1.0 0.0 250 300 350 400
Tm(ice) \°C Th(total) \°C
Fig. 6. Synoptic representation of the microthermometric properties of the aqueous FIAs from the Sigma deposit.
same suite of elements, which show narrow ranges (a)

of concentration. Sodium is the most abundant 105
fluid component in all assemblages and its total Na
range is between 1800 mg/g and 31 500 mg/g in 104 K
B
μg/g
the entire dataset (Table 5). Narrower ranges, typi- 103 As Cu

cally between 10 000 mg/g and 28 000 mg/g, were Li
102 Sr Ba
documented in individual assemblages. In addition Rb Sb
Cs
to Na, also K and B are typical components of the 10
inclusion fluids, showing ranges of 300–9500 mg/g 1
and 80 –2200 mg/g, respectively, in the dataset.
Other analytes, which have been quantified sys- (b)
tematically in a third of the assemblages (Table 5), 105
show considerably lower concentration ranges (Sr, 104 Au As
Lower Crust normalized
9–52 mg/g; Rb, 1–20 mg/g; Ba, 5–50 mg/g; and B

103
As, 80 –850 mg/g). Another group of trace ele- Sb
ments, namely Li, Cs, Cu and Sb, was determined 102 Cs
Cu
in a few assemblages and in a relatively low number 10
Li
Na Rb K
of analyses; thus, the corresponding concentration
ranges are relatively less representative of the five 1
deposits. We note that while the broad significance 10-1
of these ranges should be taken with caution, their 10-2 Sr
Ba
absolute variations are all within one order of mag-
10-3
nitude (Li, 10 –100 mg/g; Cs, 4–8 mg/g; Cu, 50–
350 mg/g; Sb, 2– 15 mg/g). This suggests a lim- Fig. 7. Compositional characteristics of the ore
ited compositional variability of orogenic fluids fluids from the studied orogenic gold deposits. (a)
in general. Concentrations of major and trace elements in FIAs from
These limited compositional variations justify the five studied orogenic gold deposits. Data show the
the evaluation of an average composition of the average composition of the 14 analysed assemblages,
entire dataset (Fig. 7a) (i.e. a model composition and the vertical bars represent the corresponding
standard deviations (1s) for each element in the whole
of the orogenic fluid that can be considered repre- dataset. The bars in K plot concentration ranges (see
sentative of the five deposits: Na, 12 300 + 7300 text). (b) Normalized compositional plot comparing the
mg/g; K, 2000 mg/g; B, 610 + 530 mg/g; Sr, average orogenic fluid with the lower Crust (data from:
26 + 12 mg/g; Rb, 10 + 5 mg/g; Ba, 20 + 10 Rudnick & Gao 2003; i.e. a potential source region of the
mg/g; As, 290 + 220 mg/g; Li, 50 + 30 mg/g; orogenic gold deposits).
Cs, 6 + 2 mg/g; Cu, 180 + 120 mg/g; and Sb, the aqueous-carbonic ore fluid). We confirm pre-
8 + 6 mg/g). Among the 31 inclusions belong- vious results showing this type of aqueous fluid
ing to five assemblages from the deepest portion being relatively rare in orogenic deposits (Robert
of the quartz-tourmaline-carbonate vein network & Kelly 1987), but this characteristic might be
of the Sigma deposit (e.g. Fig. 1c,d), ten show Au dependent on the peculiar genesis of this fluid. Fol-
concentrations between 0.5 mg/g and 5 mg/g lowing the arguments of Garofalo (2004a, b), we
(i.e. the most probable range of Au concentra- propose that the genesis of the aqueous fluid at
tion). Inclusions showing asymmetric signal struc- Sigma, and possibly in other deposits as well, is the
tures (Figs 3 & 4) give Au concentrations ranging type of mass transfer taking place between host
from 7 mg/g to 2100 mg/g and are not considered rocks and ore fluids. Garofalo (2004a) showed that
further. two types of visible hydrothermal alteration haloes
Notably, inclusions in which Au was detected developed around the Au-bearing veins of Sigma;
and measured include those of both the aqueous- a more common albite-rich type (bleaching) and a
carbonic and aqueous-fluid types and inclusions tourmaline-rich type. These two visible alteration
that homogenize both via liquid and vapour disap- types formed during multiple stages of shearing
pearance at temperatures between 350 8C and of the host rocks, opening, growth and interconnec-
410 8C. Au-rich and Au-poor assemblages are indis- tion of vein segments, and during gold precipitation
tinguishable in terms of trace element composition, within veins and the wall rock. Petrographic and
and no compositional difference between large or mass transfer constraints on these haloes showed
small inclusions is evident from the dataset. It is that they developed from distinct dissolution/
further noted that Au and B concentrations in precipitation reactions between the vein ore fluid
liquid- and vapour-rich inclusions are quite simi- and the wall rock (Garofalo 2004b). During the for-
lar. This feature is observed in only three FIAs mation of tourmaline-rich haloes, components like
(2321W, 2502WA and DH 16280-FIA8); thus, its CO2, SiO2, B, Al2O3, Na2O, CaO, S and Au were
significance cannot be generalized to the whole transferred from the vein fluid to the porphyritic
dataset. However, in light of recent experimental diorite host rock, while others like K2O and FeO
findings of high Au solubility in vapour-like geo- were transferred from the rock to the fluid. In con-
logical fluids (Hurtig & Williams-Jones 2014; Pok- trast, the formation of the albite-rich haloes took
rovski et al. 2013, for a review), this evidence is place with the transfer from the host rock to the
considered to be fundamental to define the con- vein fluid of the same components listed above,
ditions of transport and deposition of Au in oro- except for B, Au and S (i.e. bleaching formed
genic deposits. while the host rock was loosing components). This
transfer provided the vein fluid with the chemical
components that were needed for the precipita-
Discussion tion of vein tourmaline and caused the progres-
sive replacement of biotite, chlorite, epidote and
The dataset presented here provides new con- quartz of the host rock by the assemblage albite-
straints on the properties of both aqueous and pyrite-pyrrhotite. Garofalo (2004b) identified these
aqueous-carbonic fluids in orogenic deposits and combined transfers into and out of the veins as a
supplies a set of LA-ICP-MS compositional data mechanism of modification of ore fluid compo-
for these fluids from petrographically constrained sition, which must have involved both major unbuf-
samples. The following discussion considers these fered fluid components (i.e. CO2, SiO2) and minor
constraints for the five deposits and attempts a criti- and trace components like Rb, Sr, high field strength
cal evaluation of the conditions of gold transport elements (e.g. Zr, Ta, U, Th) and REE. Such a
and deposition in orogenic deposits in general. mechanism could have resulted in the formation of
batches of aqueous fluid within some sections of
The aqueous ore fluid the vein network.
This proposed genesis of the aqueous fluid is
The data gathered on the aqueous fluid inclusions consistent with the evidence for the relatively rare
of Sigma confirms the results of previous studies occurrence of hot aqueous fluid inclusions in most
whereby this fluid type transported and deposited orogenic deposits (cf. Ridley & Diamond 2000).
gold in the deposit in addition to the aqueous- Accordingly, the aqueous fluid is not abundant
carbonic fluid (Boullier et al. 1998). We show because substantial loss of CO2 from the ore
(Fig. 6, Tables 4 & 5) that the aqueous fluid has fluids demands types of fluid-rock interaction (e.g.
a bulk salinity ranging from 0.4 mass% to 4.4 tourmaline-rich alteration at Sigma) that are not
mass% NaCleq, a T h(total) of 300 –420 8C and a common. Also, the intense fluid-rock interaction
range of Au concentrations of 0.5–2.5 mg/g (i.e. that would be necessary to produce large batches
properties that are indistinguishable from those of of this fluid within the veins is dependent on a
number of geochemical constraints (wall rock com- Evidence for boiling of the ore fluid
position, P, T) that limit the amount of CO2 loss
from the fluid. Fluid-rock interaction depends also The vast majority of the studied assemblages show
on local geological factors like shear zone density variable phase ratios at room temperature (Fig. 1b,
and arrangement of vein arrays (i.e. network top- d) and opposite modes of total homogenization
ology; see fig. 3a in Garofalo 2004a). The combi- within a common range of 200–350 8C (Figs 5b,
nation of all these factors is not easy in most f, l, p, t & 6b, d, f ). These features were described
orogenic deposits, and the probability of capturing in previous studies (see Previous fluid inclusion
the aqueous fluid in a fluid inclusion sample is studies section) and were in general considered an
consequently minor. important piece of evidence for both the aqueous
It must be noted that alternative processes and aqueous-carbonic fluids being in a heterogene-
explaining the genesis of high temperature aqueous ous state at the time of entrapment (cf. Diamond
ore fluids in orogenic deposits can be considered 1990) and therefore for (liquid-vapour) phase sep-
in principle, and include for example genesis from aration controlling gold precipitation within the
a distinct source or from a pristine ore fluid chang- quartz veins (cf. Seward 1989). However, in het-
ing its composition in space and time (an ‘evolving erogeneous assemblages entrapped at equilibrium,
fluid’). While all these mechanisms are conceiv- liquid- and vapour-rich inclusions must display sys-
able, they contrast with a fundamental constraint tematic and predictable ranges of densities and sali-
provided in this study (i.e. with the evidence for nities so that the salinities of the denser liquid-rich
a compositional uniformity of the Au-transporting inclusions are always higher than those of the less
ore fluid). The narrow ranges of concentrations dense vapour-rich counterparts and agree with the
of most fluid components in the five deposits con- theoretical values determined independently from
sidered here (Fig. 7a) limit the possibility that model fluids (Ramboz et al. 1982; Bodnar et al.
coeval and compositionally distinct ore fluids were 1985; Diamond 1990). This agreement is needed
simultaneously present within the ore bodies. not only for the identification of the trapping
(a) AQUEOUS FLUID (b) AQUEOUS-CARBONIC FLUID (c)

450 40
P
30
FIA 2502 WA Liq-rich Vap-rich

DH 16280-FIA 7L
end-member end-member
DH 16280-FIA 7V
200
Fluid inclusion
vapour entrapment
apor
2321W-FIA 2V 2321W-FIA 2L Pt
400
150
ted v
T / °C
Lcar + Laq
satura
P/ MPa
halite-saturated liquid
e
urv
al c
critic Tt T
halite-
DH 16280-FIA 8V liquid
20 100
"Pt"
L-rich
350 V-rich (flinc #48)
DH 16280-FIA 8L 50 (flinc #39)
14 MPa
0.001 0.01 0.1 1 10 100 250 300 350 400 450

mass% NaCleq T / °C
Fig. 8. Properties of fluid inclusions homogenizing by liquid and vapour disappearance in individual assemblages.
(a) Bulk salinities and ranges of T h(total) of three aqueous FIAs of the Sigma deposit. These data are plotted together
with the corresponding properties of the NaCl-H2O model fluid (data from Bischoff & Pitzer 1989). The shaded boxes
report, for each indicated assemblage, the measured ranges of salinities and T h (total) of the inclusions homogenizing by
liquid or vapour disappearance. Note that inclusions having T h(total) , 350 8C are not plotted. If the assemblages were
hosting mixtures of a phase-separating aqueous fluid at equilibrium, the distribution of these properties would be
systematic and predictable, i.e. along the same isobars and at opposite sides of the critical curve. The lack of such a
distribution implies that some properties of the examined assemblages are probably spurious. (b) Estimation of the
pressure of entrapment (Pt) of the aqueous-carbonic fluid based on the isopleths of two low-T h(total) inclusions of
assemblage ‘Sigma 2502 WA’. These isopleths correspond to inclusions homogenizing by liquid and vapour
disappearance at 221 and 219 8C, respectively, and should approach those of the liquid- and vapour-rich end-member
fluids. They have been calculated using the equation of state of Duan et al. (1995) for the H2O-NaCl-CO2 system using
the ‘Geofluids Model 1’ (available at: http://geotherm.ucsd.edu). Because the isopleths are very similar, and do not
intersect each other at one point (compare with inset in (c)), we conclude that their properties are not those of immiscible
pairs. (c) Schematic P-T projections of isopleths of liquid-rich and vapour-rich fluid inclusions from a heterogeneously
trapped aqueous-carbonic fluid at equilibrium (modified from Diamond 2003). The two isopleths correspond to L- and
V-rich inclusions having the lowest T h(total) in a hypothetical ideal assemblage, i.e. they identify the liquid and vapour
end members of the phase-separating aqueous-carbonic fluid.
temperatures and pressures (given by the low- changes in lithostatic pressure show that the con-
Th(total) inclusions; Roedder & Bodnar 1980) but ditions of low strain typical of natural quartz do
also to exclude spurious data that may result from not result in the systematic modification of com-
post-entrapment re-equilibration. Figure 8 shows positions and densities of the host fluid. These
this type of analysis for two assemblages of the data show that FIAs selected from undeformed (or
Sigma deposit hosting both aqueous and aqueous- slightly deformed) vein samples preserve some
carbonic ore fluids, and shows that the fluid proper- unmodified inclusions whose properties remain
ties cannot strictly be considered as indicative of unperturbed after re-equilibration (Bodnar 2003b,
phase separation. The same analysis for assem- for a review; Diamond et al. 2010). In our sample
blages from Berezovskoye, Red Hill and Pestarena set, the highest number of precursor inclusions is
brings us to the conclusion that phase separation probably found in the FIAs Sigma 2321W-FIA3
cannot be rigorously demonstrated in these deposits. and Wattle Gully SG1-FIA1, for which total
We note that this inconsistency does not exclude homogenization occurred systematically by bubble
the possibility that the ore fluids of the five depos- disappearance at 314 + 39 8C and 197 + 3 8C,
its were phase separating at the time of gold respectively (Table 4). The properties of these
deposition, but simply that the conditions at which fluids at entrapment can be estimated with the clas-
this process took place cannot be easily determined sic method shown in Figure 9, which combines
from our samples with a high level of confidence. the range of calculated isochores with the exper-
There are two plausible explanations for the incon- imentally determined two-phase fields of model
sistencies of Figure 8, namely (a) the possibility that fluids and the geothermal gradients of the Lachlan
the analysed samples were subjected to a degree of fold belt and Archean Superior Province. At
post-entrapment re-equilibration, and (b) the possi- Wattle Gully (Fig. 9a), the combination of these
bility that the model fluids used for comparison are constraints defines the entrapment conditions at
inappropriate. Considering the evidence for a dom- c. 250–450 8C and 200–380 MPa, which are very
inance of Na and CO2 in the ore fluids derived from close to the 300 8C/130 MPa previously estimated
LA-ICP-MS and Raman spectroscopy, it is improb- for the deposit (Cox et al. 1995). The most signifi-
able that H2O-NaCl and H2O-NaCl-CO2 model cant difference with the previous study regards the
fluids are inappropriate for the inclusions studied pressure range, which was calculated by Cox et al.
here. Hence, the most probable process that gener- (1995) using the H2O-NaCl model fluid (i.e.
ated the determined spread of inclusion properties neglecting the effect of CO2 content on the fluid
is considered to be minor post-entrapment re- pressure). We interpret our values as the closest to
equilibration. Two observations from our database the vein formation conditions at Wattle Gully,
are consistent with this conclusion. The first is the which were close to boiling. The properties of the
petrographic evidence for at least some degree of ore fluid within Sigma 2321W-FIA3 do not allow
intracrystalline deformation and re-crystallization good constraints because the slopes of isochores,
of the host quartz even in our best euhedral and two-phase field and geothermal gradient are sim-
least deformed samples (Fig. 1c). The second is the ilar to each other. Thus, our data provide only a
evidence for similar ranges of T h(CO2), Tm(Cla) minimum trapping temperature from the T h(total)
and Tm(Ice) in fluid inclusions belonging to the data. For the following considerations on fluid-
same assemblage and showing opposite modes of mineral equilibria, we define a T of 350 8C and a
homogenization (Table 4). These observations are Ptotal of 200 MPa as adequate to constrain the con-
independent of any consideration of the equations ditions of Au precipitation in this deposit.
of state used to derive fluid properties.
From a practical standpoint, the tests shown in Composition of the ore fluid
Figure 8 indicate that FIAs of orogenic deposits
collected after considerable petrographic selection An important first result of this study is the evi-
might not necessarily define precise fluid proper- dence for a uniform composition of both aqueous
ties. This claim may appear daunting, as it might and aqueous-carbonic fluid inclusions in the Au-
imply that these fluid inclusions do not obey the fun- mineralized veins. This shows that, despite the
damental assumptions of most studies (i.e. fluid important differences in terms of microthermomet-
inclusions are closed isochoric systems after entrap- ric properties and volatile contents, the two types
ment; see Roedder 1984) and that their properties of ore fluid transport similar contents of major and
might be consequently miscalculated. However, trace elements. A second result of this study is
experimental work carried out with the aim of deter- more general and deals with the unexpected compo-
mining the morphological (Vityk & Bodnar 1995; sitional similarity between ore fluids forming depos-
Tarantola et al. 2010) and compositional (Vityk & its with different geological settings. These two
Bodnar 1998; Diamond et al. 2010) changes of results indicate that a unique Au-transporting fluid
fluid inclusions subjected to deviatoric stress or to generated the ore bodies independently from their
(a) those measured in other samples as an indication

Wattle Gully of, at most, minor post-entrapment modifications.
1000 A second corollary hinging on our results is that
800 mixing of aqueous and aqueous-carbonic fluids
SG1 isochores within the shear zone networks would not cause
P \ MPa
600 significant order-of-magnitude chemical modifica-

tions to the ore fluid, in particular to the Au bud-
400 get (see below). Thus, the fundamental control on
geothermal
200 gradient Lachlan belt the chemical signature of orogenic fluids is probably
found in the process(es) occurring in the source
regions of the deposits.
100 200 300 400 500 600 Another result of our study is that the concen-
trations of the suite of elements (Fig. 7a) are distinct,
(b) Sigma compared to compositions of other well-defined
1000 reservoirs. For instance, compared to the late-stage
Archean geothermal (low to intermediate salinity) aqueous ore fluid
800
gradient forming porphyry Cu( –Mo– Au) and skarn deposits
P \ MPa
600 at 150–450 8C (Kouzmanov & Pokrovski 2012, for

a review), the average orogenic fluid shows concen-
400 trations of Na, K, Au and Cu that are of the same
200 ochores order of magnitude. However, Fe, Zn, Mo and Ag
2321W is are important components in late-stage porphyry
fluids, but in the orogenic fluid they are undetected.
100 200 300 400 500 600 Similarly, the concentrations of Mn and Pb in the
late-stage porphyry fluids vary between c. 150 mg/g
T \ °C and c. 1000 mg/g but are 2 orders of magnitude
Fig. 9. Calculated isochores of samples Wattle Gully lower in the average orogenic fluid. It must be
SG1 (a) and Sigma 2321 W-FIA 3 (b), and comparison noted that, among our analysed trace elements, Cu
with the approximate geothermal gradients of the is known for showing a clear tendency to become
Lachlan belt and Superior Province at the time of ore enriched in vapour-rich inclusions due to post-
formation. The isochores have been calculated using the entrapment diffusion (Lerchbaumer & Audétat
‘Isoc’ software of Bakker (2003), which combines the 2012). This process takes place at magmatic temp-
approach of Bowers & Helgeson (1983) and Bakker eratures (800 8C) and may not be representative of
(1999) to isochore calculations. The 35– 45 8C/km
gradient of the Lachlan belt in (a) is consistent with the
the orogenic environment. The narrow range of Cu
supposedly hot conditions of the belt during ore concentrations in the dataset is exclusively of
formation (Collins et al. 2004). The geothermal gradient liquid-rich inclusions and, while limited, implies
of the Archean Superior Province (b) was calculated that important compositional modifications from
using the parameters given by Rudnick et al. (1998) for post-entrapment re-equilibration can be excluded
cratonic geothermal calculations. The thick curve in (a) in our samples.
is the two-phase field of an H2O-NaCl-CO2 fluid having A fundamental difference between orogenic
4.8 wt% NaCl (Diamond 2003). The thick curve in (b) fluids and magmatic-hydrothermal fluids in gen-
was calculated with the SoWat software (Driesner 2007) eral is the evidence for significant compositional
and shows the two-phase field of an H2O-NaCl fluid
having 1.7 wt% NaCl.
variations found in the latter (≥2 orders of magni-
tude for Cu, Mo, Ag, Pb, Zn; see Kouzmanov &
Pokrovski 2012). In magmatic-hydrothermal fluids,
metal concentrations vary due to aqueous fluid/
geological settings and age, depth of formation, tim- silicate melt partitioning at magmatic conditions,
ing of Au precipitation (i.e. timing of fluid inclusion as demonstrated by a number of experimental
entrapment; Fig. 1), type of host rocks and local studies (e.g. Zajacz et al. 2008). This fundamental
fluid-host rock interaction processes. control is particularly evident when fluid inclusion
A first corollary of this later result is that compositions are normalized against the average
our compositional data reflect probably the true Crust composition, which highlight enrichment
ore fluid composition, as post-entrapment re-equili- factors of 10–1000 for Cu, Mo, Pb, Zn, Sb, As
bration would have conceivably generated a large and Au. In orogenic deposits, the same normali-
compositional spread in the dataset. In partic- zation (Fig. 7b) shows that only Au, B, As and
ular, we consider the consistency between the Au Sb are significantly enriched in the inclusion fluids
concentrations measured in the least deformed with respect to the Crust (enrichment factors
assemblages (from sample Sigma 2321W) and c. 80–1600), demonstrating that orogenic fluids
are much more specialized in terms of element may not be equally important for the generation of
transport, and that Au is the only ore metal that is orogenic fluids.
transported effectively. Only a few other metals One composition that is comparable with the one
moderately enrich orogenic fluids with respect to reported here is that defined with crush-leach ana-
the Crust (Cs, Cu, Li; enrichment factors: 4–19), lyses for the orogenic deposit of Brusson in the
while the others show a crustal signature (alkalis) Western Alps (Yardley et al. 1993). The Brusson
or are depleted (Sr, Ba). Notably, the enrichment data show important similarities with our data set
factors for Au, B, As and Sb are independent of in terms of concentrations of some major and trace
the crustal reference composition used for nor- elements (Na, K, B, Sr, Ba, As).
malization (i.e. average, lower, or middle Crust), Finally, our data do not show a clear compo-
showing that they define a clear characteristic of sitional difference between the fluid inclusions of
orogenic fluids. the barren quartz-tourmaline Audet vein (outcrop-
The factors controlling these enrichments are ping a few km from the Sigma deposit) and those
those controlling the stability of the Au-, As-, B- of the Au-rich quartz-tourmaline veins from under-
and Sb-transporting complexes in hydrothermal ground productive levels (Table 5). From this evi-
fluids, which were recently established experimen- dence we infer that some unexplored sections of
tally for a limited range of conditions similar to the Audet vein could be indeed productive, but
those of orogenic deposits (Pokrovski et al. 2005; lack of a comprehensive dataset from other barren
Williams-Jones & Heinrich 2005; Foustoukos & veins outcropping further away from the Sigma
Seyfried Jr 2007; Pokrovski et al. 2008; Pokrovski deposit (or even outside the Val d’Or camp) make
et al. 2013). These studies showed that exactly this claim only a working hypothesis.
this suite of elements is the most volatile amongst
the ore forming metals and metalloids between Ore fluid properties from fluid-mineral
200 8C and 500 8C, and that volatility is due to the equilibria
stability of hydrated species in the vapour phase.
The extent to which the measured range of concen- Thermodynamic equilibria between ore fluid and
trations of these elements in our samples can be vein minerals at 350 8C and 200 MPa allow cal-
explained by variations in the stability of vapour culations of fluid properties at gold deposition
complexes will be discussed below. Here, we note and provide additional insights into the mecha-
that our dataset provides only a dataset on Au nisms of deposition. Properties have been com-
and B concentrations in coexisting vapour- and puted considering the Au-rich H2O-NaCl-CO2 ore
liquid-rich inclusions. Hence, a detailed evalua- fluid of Sigma and a model vein assemblage made
tion of the transport conditions of As and Sb in of quartz-albite-tourmaline-muscovite-biotite-pyrr-
orogenic fluids is difficult with the current data. hotite-pyrite. The pyrite-pyrrhotite equilibrium
Some key compositional differences also allows the bracketing of logaH2S and logaO2 in
exist between orogenic and metamorphic fluids. the ore fluid, which are constrained between 21.9
Crush-leach compositional data on fluid inclusions and 21.1 and 233.0 and 233.9, respectively (Fig.
entrapped at 220– 260 8C within quartz veins of 10a). The resulting range of S concentrations in the
various metamorphic terranes showed that meta- aqueous and aqueous-carbonic fluids is between c.
morphic fluids may have Ca and Sr concentrations 4500 mg/g and 6400 mg/g. Equilibrium between
varying between hundreds and tens of thousands vein albite and muscovite constrains the range of
of mg/g (Yardley 2005), which is several orders of aNa+/aH+ at values that are always higher than
magnitude higher than what is documented in oro- those of aK+/aH+ (Fig. 10b). The pH of the ore
genic fluids (Fig. 7a). Laser Ablation-ICP-MS of fluid in the veins is buffered by this equilibrium, and
fluid inclusions forming at 250 –320 8C within we calculate a range of 4.6–5.3 from the range of Na
quartz crystals of Alpine fissure veins showed con- and K concentrations in the fluid inclusions. Note
centrations on the order of tens of mg/g for As, Sb that this pH range corresponds to slightly acidic to
and Cu in metamorphic fluids (Miron et al. 2013). neutral fluid conditions (at 350 8C and 200 MPa,
These concentrations are one order of magnitude neutrality is reached at pH c. 5.1), which provide a
lower than those we determined in orogenic fluids fundamental constraint on Au transport (e.g.
for the same elements. These compositional differ- Seward 1981; Seward 1984).
ences suggest that the processes considered impor- Additional indirect information about fluid pH is
tant for the generation of metamorphic fluids (i.e. given by precipitation of albite outside the veins
the chemical equilibration of pervasive basinal within the albite-rich hydrothermal alteration
brines with their host rocks at various (peak or retro- haloes. Within such haloes, albite precipitates in
grade) metamorphic conditions (Yardley 2005) or equilibrium with muscovite from the interaction
the local dehydration of rock sequences during between a vein fluid, initially undersaturated, with
retrograde metamorphism (Miron et al. 2013)) quartz and the host rock. Figure 10b shows that
(a) (b)
-28
350 °C 5 350 °C log aSiO2(aq)
Hematite Pyrite 200 MPa 200 MPa -1.6
XCO2 = 0.03 -1.5
log (aNa+/aH+)
-30 Albite
XCH4 = 0.01
ai = mi 4
log aO2
Microcline
-32 Sigma Sigma
Paragonite ore fluid
Magnetite ore fluid
CO2 3
-34
CH4
Pyrrhotite Pyrophyllite Muscovite
-36 2
-4 -3 -2 -1 0 2 3 4 5
log aH2S log (aK+/aH+)
(c) (d)
-25 350 °C
HSO4-
SO42-
350 °C
4 K-Feldspar 200 MPa 200 PMa
estimated Btot: Stot = 0.032 m
log (aK+/aH+)
50-1100 ppm Hematite

Muscovite
-30
3 Magnetite
log aO2
Phlogopite Sigma
1p
log aB(OH)3(aq) ore fluid
pm
Pyrite
Clinochlore
0
100
-35 Pyrrhotite
-2.
2
5
-2.
pp
-3.
10
b
pp
H 2S
Andalusite
b
HS-
1 dravite + albite
-40
3 4 5 6 2 4 6 8
log a Mg2+/a (H+)2 pH
Fig. 10. Calculated silicate vein equilibria and gold solubility at 350 8C and 200 MPa, i.e. at the estimated conditions
of Au deposition in the Sigma deposit. (a) Stability of the pyrite-pyrrhotite association in the veins and superimposed
CO2-CH4 equilibrium as determined from fluid inclusion data. These data provide constraints for the oxidation state
and the total sulphur concentration in the ore fluid. (b) Equilibria of Na- and K-silicates in the quartz-tourmaline veins.
The shaded field highlights the activity ratios of the vein fluid, which was combined with LA-ICP-MS data to constrain
fluid pH. The dashed lines contour the positions of the various equilibria at different log units of SiO2(aq) activity.
The point on the albite field is consistent with albite-muscovite equilibrium with a silica-undersaturated fluid.
Such a fluid would precipitate albite as it dissolves quartz from the visible alteration halo. (c) Equilibrium of the
assemblage quartz-tourmaline-albite-muscovite-biotite in the deepest veins of Sigma. The stability field of
dravite + albite is contoured onto that of muscovite and biotite as a function of activity of boric acid. (d) Solubility of Au
in Sigma ore fluid shown as concentrations of hydrogen sulphide aqueous complexes. The shaded box marks the
estimated ranges of logaO2 and pH of the ore fluid, which correspond to a contoured range of Au concentration of
c. 20–100 ng/g.
such a fluid would precipitate albite as it dissolves the ore fluid between 22.3 and 22.0 (Fig. 10c),
quartz from the wall rock to achieve saturation. In which correspond to a range of B concentrations
principle, this process might involve pH changes of c. 50 mg/g to 1100 mg/g. This value is very
and foster gold precipitation. similar to that measured in the Sigma ore fluid (B:
The stability of tourmaline and other K- and 80 –2200 mg/g, Table 5) and leads to the conclu-
Mg-bearing silicates in the veins provide an addi- sion that tourmaline precipitation took place at, or
tional constraint on the logaK+/aH+ and on the close to, equilibrium within the veins.
logaMg2+/(aH+)2. The co-existence of tourmaline The ranges of pH, logaO2 and Stot concen-
and biotite in the deepest veins of Sigma (Robert tration in the ore fluid predict a gold solubility
& Brown 1986b) predicts logaB(OH)3(aq) values of of c. 0.02–0.1 mg/g in the Sigma ore fluid (Fig.
10d), which is lower than the range of gold concen- of density ratios of the liquid and vapour phases.
trations in the fluid inclusions (Au ¼ 0.5–5 mg/g). The data show that Au may fractionate consider-
This difference between theoretical and measured ably into the S-rich vapour phase of a hydrother-
Au concentrations can be explained by several mal fluid at the indicated conditions, and that this
factors, the first of which could be a degree of fractionation increases when the density difference
error in the pH estimation of the ore fluid based on between vapour and liquid phase decreases. This
fluid-mineral equilibria (Fig. 10b, c). For instance, is due to the stability in a dense vapour phase of
a fluid pH of 5.5 (i.e. only slightly higher than the species formed from the neutral aqueous AuHS0
value we estimate) would correspond to an Au solu- (e.g. Au(HS)H2S0; Pokrovski et al. 2013). Note
bility .0.1 mg/g and would bring some overlap that aqueous (i.e. S-free) ore fluids at the same con-
between measured and predicted solubilities. Such ditions fractionate much less Au into the vapour
a small difference is probably compatible with the phase (Fig. 11, shaded area), demonstrating that
uncertainty associated with the thermodynamic Au volatility in hydrothermal fluids is strongly
properties of Na-, K- and Mg silicates in our calcu- dependent on the presence of S irrespective of
lations. Another factor is provided by the possible fluid pH.
presence of additional Au complexes in the orogenic Our data show that the volatility of Au in the
ore fluid. As suggested in the previous section, at Sigma ore fluid was probably high at the time of
350 8C and at a pH , 5 (i.e. at conditions very ore formation, as two FIAs show very similar Au
close to those calculated for Sigma) experimental concentrations in the dense vapour- and liquid-rich
data show that S-bearing Au-transporting hydro- inclusions. This is graphically shown in Figure 11
thermal fluids are distinctly volatile due to the pres- by the position of the two assemblages close to
ence of stable Au-sulphide species in the vapour the critical point and slightly above the zero frac-
phase (Pokrovski et al. 2013, for data review; tionation line (Km ¼ 1). In light of the experi-
Pokrovski et al. 2005, 2008; Williams-Jones & mental relationships described above, we conclude
Heinrich 2005). Such volatility is evident in that the measured vapour/liquid fractionation of
Figure 11, which plots the experimental data of Au at Sigma can be explained by the presence of
vapour/liquid fractionation (squares) as a function neutral Au-sulphide species in the vapour phase,
1.0
0.0 C.P.
log10 Km (mvap/mliq)
B
-1.0
-2.0
Pokr. et al. (2008)
-3.0 Au Au: 2502WA
Au: DH 16280 - FIA 8
-4.0
B: 2321W - FIA 2
-5.0
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
log10 (ρvap/ρliq)
Fig. 11. Partitioning of Au (circles) and B (triangle) between vapour- and liquid-rich fluid inclusions of two
assemblages from the Sigma deposit. These data are plotted as a function of density ratios of the inclusion phases and are
compared with experimentally determined Au-partitioning data in S-bearing fluids at 345– 350 8C and pH ,5 (squares,
from Pokrovski et al. 2008). They are also compared against the theoretical partitioning of Au and B in S-free aqueous
fluids (shaded areas, from Pokrovski et al. 2005; Pokrovski et al. 2013).
which are not considered in Figure 10d (consider- the typical ore bodies, and corresponds probably to
ing only aqueous species) and for which no HKF- the mid-lower crust. After formation, an orogenic
equation-of-state parameters are presently avail- fluid travels through the crust within its shear-zone
able. Hence, our reported discrepancy between network up to the depositing sites while interacting
measured and predicted concentrations might with the host rocks, modifying in part its source
rather reflect the present difficulty in considering major and trace element signature. A large pro-
the vapour species in an equilibrium model, rather portion of this fluid probably remains focused
than the overestimation of Au concentrations. Other within the host network and does not develop sub-
Au-transporting complexes that are probably vertical mineral and metal zoning (cf. Groves
present in orogenic fluids, but that cannot be et al. 2003; cf. Ridley et al. 1996).
included in current thermodynamic models, are the Past studies identified several mechanisms of Au
Au-polysulphide aqueous complexes from the tri- precipitation in orogenic deposits based on a
sulphur ligand S2 3 (Pokrovski & Dubrovinsky number of types of geochemical and geological evi-
2011). These complexes are not considered in our dence. These studies considered boiling, wallrock
calculations, but at 350 8C and 200 MPa they are sulphidation, and fluid mixing as the most probable
most probably present and stable (Pokrovski & Au-precipitating mechanisms (e.g. Goldfarb et al.
Dubrovinsky 2011), suggesting that an additional 1988; e.g. Mikucki 1998). Our Au-fluid data, in
contribution from these compounds to the bulk combination with geological constraints on the
Au solubility should be accounted for. five deposits considered here, indicate that a combi-
Notably, a comparison between our analytical nation of fluid decompression and boiling might
data and those on the volatility of metalloids in control Au grade distribution in orogenic deposits.
hydrothermal fluids (Pokrovski et al. 2013) shows Such a control is exerted via the modification of
that the same considerations on vapour speciation the stability of both aqueous and volatile complexes
may be applied to B as well. In one aqueous assem- of Au (and probably of B, As and Sb) present in the
blage of Sigma (2321W-FIA 2), we measured B ore fluid. Current knowledge of the effects of
concentrations in vapour-rich inclusions that are pressure variations on the stability of volatile com-
very similar to those of the liquid-rich counterparts plexes is limited but consistently indicates that a
(615 v. 450 mg/g, respectively). These concen- decrease of fluid pressure (i.e. density) causes a
trations correspond to a fractionation factor higher decrease in the fractionation of Au into the vapour
or close to one (Fig. 11), (i.e. very similar to the phase (Pokrovski et al. 2013; Pokrovski et al.
equilibrium vapour-liquid partitioning determined 2014). Thus, the lower the pressure, the lower the
experimentally for B in aqueous fluids at c. 350 8C amount of Au that can be dissolved in a vapour-solid
(e.g. Pokrovski et al. 2013)). This indicates that an system. As an example of this pressure control,
aliquot of this element was transported in the ore experimental data show that a decrease of c. 10%
fluid as a vapour species (presumably as B(OH)3) of vapour density at 350 8C and pH c. 5 causes a
and implies that the predicted ranges of B concen- decrease of vapour/liquid partitioning of Au by
trations in the Sigma fluid (Fig. 10c), based only greater than two orders of magnitude (Fig. 11).
on contributions of aqueous species, underestimate Such a decrease is essentially due to the diminished
the true bulk concentrations. aptitude of a low-density vapour to transport metals
Thus, considerations on Au and B solubilities (with or without S) and indicate that orogenic fluids
in hydrothermal fluids lead to the hypothesis that having a significant fraction of hot, dense and S-
the vapour phase of orogenic fluids may transport rich vapour (like the one documented in the Sigma
a relevant proportion of these elements at condi- deposit) might experience substantial Au deposi-
tions that closely approach equilibrium with the tion when subjected to decompression. This is a
vein minerals. The mechanisms that controls Au fundamental result, as it shows that fluid pressure
(and vein mineral) precipitation are best con- has an important role in controlling Au precipi-
strained by a combination of geological and geo- tation from orogenic fluids, providing a conceptual
chemical evidence. link between the geochemical processes that con-
trol Au solubility in geological fluids and the well-
documented structural control of Au occurrence
A model of gold precipitation in orogenic in orogenic deposits. Within these deposits, the
deposits volumes where gold grades are the highest are in
general vein intersections (Cox et al. 1995; Allibone
Our data indicate that a unique and recurring geo- et al. 2002; Garofalo et al. 2002). In these specific
logical process generated (and generates) orogenic deposit areas, multiple events of vein opening and
Au fluids at different times in different active conti- sealing are typically documented by high vein
nental margins. This process must occur at a crustal density, crack-seal textures, and increased vein
depth that is for sure greater than the palaeodepths of thickness. A combination of this evidence with the
experimental evidence for Au precipitation by would cause the vein fluid to expand to very low-
vapour decompression lead to the conclusion that density values and almost zero pressure (Weather-
vein interconnections probably represent the loci ley & Henley 2013). These extreme pressure
where such decompression takes place. Gold pre- variations imply very large variations of some key
cipitation (but probably also precipitation of physical-chemical properties of the ore fluid (i.e.
quartz, tourmaline and As and Sb minerals) at vein pH, oxidation state, etc.) including the bulk chemi-
interconnections may therefore be triggered by mul- cal composition, none of which is evident from
tiple events of transient decompression of a dense our data.
vapour-like fluid.
We note that fluid decompression as described
above is conceptually distinct from boiling, as it Volume constraints on orogenic fluids
occurs in fluids that are already two phase before Additional quantitative constraints on orogenic
the time of gold precipitation (Pokrovski et al. fluids can be gained by combining our compo-
2013; Pokrovski et al. 2014). We propose that sitional data with the previous mass estimates of
boiling and decompression go hand in hand in oro- vein minerals and Au accumulated in fracture net-
genic deposits, and that the first process is functional works. 3D geometrical reconstructions of the
to the generation of a compressible vapour within quartz-tourmaline vein network of the Sigma
the shear zone networks. Such a vapour would deposit allowed Garofalo et al. (2002) to calculate
be capable of transporting large quantities of Au a total volume of tourmaline of 0.4 × 106 m3,
up to the areas of vein interconnections of the vein which corresponds to c. 71 500 t of B deposited
network, and precipitate it during multiple events within the entire deposit. Combining that mass of
of vein opening. Past experimental work estab- B with our concentration range of B in the Sigma
lished that boiling itself is a very important Au- fluid inclusions (80 –2200 mg/g), we calculate that
precipitating mechanism in hydrothermal fluids, a minimum volume of hydrothermal fluid of at
due to the fractionation of volatile species like least 0.04 –1.0 km3 (with a salinity of 3 wt% NaCl
H2S and CO2 into the vapour phase and to the and a r ≈ 0.9 gcm23 at 350 8C and 200 MPa)
consequent breakdown of the hydrogen sulphide must have passed through the Sigma vein network
aqueous complexes that transport Au (Heinrich at the time of tourmaline deposition. This is the
2007, for a review; Seward 1989, 1993). However, range of fluid volume that would precipitate tourma-
this latter mechanism is efficient in fluids having line in the veins with 100% efficiency and is there-
relatively low temperatures (T , 300 8C) and press- fore only a minimum estimate of the Sigma ore
ures in which the vapour density is too low for sig- fluid. Interestingly, combining the 358 metric tons
nificant Au partitioning (Pokrovski et al. 2014). As a of historical Au production of Sigma (Gosselin &
consequence, boiling of hot (T . 300 8C) and dense Dubé 2005) with the 0.5–5 mg/g range of Au con-
orogenic fluids is most probably not very efficient in centrations in the fluid inclusions, we calculate
depositing Au due to the much higher degree of ion a second estimation of minimum fluid volume of
association and much lower dielectric capacity of 0.08 –0.8 km3, which is indistinguishable from the
water as a solvent under these conditions (Pokrovski range reported above. Notably, these results do not
et al. 2005, 2013). We stress that this proposed com- change substantially if a precipitation efficiency of
bination of boiling and decompression of orogenic 50% or less is considered. Therefore, we surmise
fluids in the range of temperatures of orogenic that the generation of a single world-class ore body
fluid flow might explain the difference between requires probably a fluid volume of 1–2 km3. Our
world-class deposits and less productive deposits: mass balance results provide an indication that
however, this is an hypothesis that needs to be only relatively small volumes of Au-transporting
tested by future research. The cumulative effects ore fluids need be discharged from orogenic belts
of boiling and decompression might also explain to form the deposits. This result contrasts with
why fluid inclusion data from high-T orogenic the massive synmetamorphic dewatering scenarios
deposits provide ambiguous evidence for boiling of previous workers based on the solubility and
(Fig. 8), while low-T deposits provide unambiguous volume of quartz in the veins (Phillips 1986; Cox
evidence (Diamond 1990). et al. 1991; cf. Ridley & Diamond 2000).
Finally, we note that the model proposed
here is fully consistent with the fault-valve model
proposing Au transport and deposition during seis- Conclusions
mogenic fault failure and transient variations of
fracture permeability (Sibson et al. 1988; Cox The evidence for a chemically uniform and special-
2005). In contrast, it contradicts the ‘flash vapouri- ized ore fluid transporting and precipitating Au
zation’ model whereby Au deposition would be from both vapour and liquid phases close to equili-
achieved by extreme fluid decompressions, which brium with the vein minerals represents a distinct
characteristic of the orogenic deposits studied here, Bierlein, F. P., Foster, D. A., McKnight, S. & Arne,
and probably also for others. This feature, together D. C. 1999. Timing of gold mineralisation in the Bal-
with the relatively modest flux of ore fluid indicated larat goldfields, central Victoria: constraints from
by our mass balance constraints, is probably a key 40Ar/39Ar results. Australian Journal of Earth
Sciences, 46, 301– 309.
genetic ingredient for this type of Au deposit and Bischoff, J. L. & Pitzer, K. S. 1989. Liquid-vapor
provides constraints on future genetic models. The relations for the system NaCl-H2O: summary of the
definition of the ultimate source of the orogenic P-T-x surface from 3008 to 500 8C. American
fluid is beyond the scope of this work, as a more Journal of Science, 289, 217 –248.
extensive and integrated database on these fluids is Bistacchi, A. & Massironi, M. 2000. Post-nappe brittle
still needed. However, our data indicate that the tectonics and kinematic evolution of the north-western
source of Au is most probably also the source of Alps: an integrated approach. Tectonophysics, 327,
the associated B, As and Sb in the fluid, a character- 267–292.
istic that might represent another direction of Bodnar, R. J. 1993. Revised equation and table for deter-
mining the freezing point depression of H2O-NaCl
future research. solutions. Geochimica et Cosmochimica Acta, 57,
683–684.
This work is a contribution to the International Geoscience Bodnar, R. J. 2003a. The origin of fluid inclusions. In:
Programme IGCP-540 (2007– 2012). The authors thank Samson, I., Anderson, A. & Marshall, D. (eds)
C. H. Heinrich and T. Pettke for inspiring discussions in Fluid Inclusions: Analysis and Interpretation. Minera-
the earlier years of this work. G. Pipino from the ‘Museo logical Association of Canada, Vancouver, Canada,
Storico dell’Oro Italiano’ is thanked for providing histori- 11–18.
cal production data on Pestarena. Critical reviews by Bodnar, R. J. 2003b. Re-equilibration of fluid inclusions.
G. B. Pokrovski and A. Hofstra are greatly appreciated. In: Samson, I., Anderson, A. & Marshall, D. (eds)
Careful final reading by J, Ridley improved the manuscript Fluid Inclusions: Analysis and Interpretation. Minera-
further. Funding from Placer Dome Ltd., ETH Zurich and logical Association of Canada, Vancouver, Canada,
the Swiss National Science Foundation to PSG during 213–230.
several years is acknowledged. Bodnar, R. J., Reynolds, T. J. & Kuehn, C. A. 1985.
Fluid-inclusion systematics in epithermal systems.
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Physical-Chemical Properties and Metal Budget of Au-Transporting Hydrothermal Fluids in Orogenic Deposits

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Physical-Chemical Properties and Metal Budget of Au-Transporting Hydrothermal Fluids in Orogenic Deposits

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org/ at CAPES-UNIVERSIDADE FEDERAL DE MINAS

Physical-chemical properties and metal budget of Au-transporting

Table 2. Characteristics of samples used in this study

Deposit Sample name Characteristics

*Samples provided by V. Yu. Prokof’ev (Russian Academy of Science).

Table 3. Characteristics of the studied fluid inclusion assemblages

Deposit Sample No. of No. Fluid Paragenetic relations

Berezovskoye Cryst 1 52 No apparent relations with Au deposition

*, Lattanzi et al. (1989).

Downloaded from http://sp.lyellcollection.org/ at CAPES-UNIVERSIDADE FEDERAL DE MINAS

GERAIS on June 26, 2015

inclusions has to be considered lower due to reflec-

Spindle stage determinations

Sample FIA # No. of Na K B Au As Sr Ba Rb Cu Mg Li Cs Mn Sb Pb

AU-TRANSPORTING HYDROTHERMAL FLUIDS

GERAIS on June 26, 2015

the ablation yield of the internal standard relative to

25 tip 30 FIA 2 FIA 1 tip core

same suite of elements, which show narrow ranges (a)

the entire dataset (Table 5). Narrower ranges, typi- 103 As Cu

9–52 mg/g; Rb, 1–20 mg/g; Ba, 5–50 mg/g; and B

(a) AQUEOUS FLUID (b) AQUEOUS-CARBONIC FLUID (c)

FIA 2502 WA Liq-rich Vap-rich

0.001 0.01 0.1 1 10 100 250 300 350 400 450

(a) those measured in other samples as an indication

600 significant order-of-magnitude chemical modifica-

600 at 150–450 8C (Kouzmanov & Pokrovski 2012, for

50-1100 ppm Hematite

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