229 257

©2013 Society of Economic Geologists, Inc.
Economic Geology, v. 108, pp. 229–257
A Fluid Inclusion and Stable Isotope Study at the Loulo Mining District,
Mali, West Africa: Implications for Multifluid Sources in the
Generation of Orogenic Gold Deposits
DAVID M. LAWRENCE,1,†,* PETER J. TRELOAR,1 ANDREW H. RANKIN,1 ADRIAN BOYCE,2 AND PAUL HARBIDGE3
1 School of Geography, Geology and the Environment, Centre for Earth & Environmental Science Research, Kingston University,
Penrhyn Road, Kingston upon Thames, London, UK, KT1 2EE
2 Scottish Universities Environmental Research Centre, East Kilbride, Glasgow, Scotland, G75 0QF
3 Randgold Resources Ltd, Halkett Street, St Helier, Jersey, Channel Islands, JE2 4WJ
Abstract
The world-class Loulo mining district (15.5 Moz resource), in the Birimian terrane of western Mali, contains
a range of mineralogically diverse styles of orogenic gold mineralization. The district is distinguished by As-rich
orebodies as at Yalea, as well as tourmaline-bearing, Fe-rich, orebodies as at Gara. New fluid inclusion and sta-
ble isotope data presented here constrain the nature of the hydrothermal fluids responsible for these different
types of mineralization, and point towards the role of multifluid sources (metamorphic and magmatic) in the
formation of orogenic gold deposits.
Microthermometric and laser Raman studies from Yalea Main and two other similar orebodies (Loulo-3 and
Baboto) reveal the dominance of coexisting CO2-N2±CH4 (type 1) and H2O-NaCl (type 2) fluid inclusions.
These inclusions show evidence of fluid unmixing from reduced (quartz-faylite-magnetite, QFM, buffered),
low-salinity (≤10 wt % NaCl equiv), CO2-rich-H2O-NaCl-N2 ± CH4 primary ore fluids. The combination of
microthermometric data and geothermometry based on ore and alteration assemblages indicate trapping tem-
peratures and pressures of 270° to 340°C at 1.4 to 1.8 kbar. The P-T-X state of the Yalea-style mineralizing flu-
ids, along with the δ18Ofluid compositions of 8.8 to 10.7‰, is consistent with the derivation of auriferous fluids
during greenschist facies regional metamorphism of the host terrane. Similar fluid compositions were previ-
ously reported elsewhere in the Birimian crust of West Africa and in other orogenic gold districts worldwide.
The precipitation of gold from the H2S-rich metamorphic fluid is primarily linked to phase separation of the
ore fluid, which is controlled by P-T fluctuations and/or fluid-rock interaction with carbonaceous host sedi-
mentary rocks (confirmed by low δ13C values of –21.7 to –15.8‰).
Fluid inclusion investigations from Gara and a similar style orebody (Yalea North) indicate the presence of
coexisting CO2 ± N2 ± CH4 (type 1) and mixed-salinity (5–21 wt % NaCl equiv) CO2-rich-H2O-NaCl inclusions
(type 3). Inclusion assemblages also contain common oxidized (hematite-magnetite, HM, buffered), high tem-
perature (>400°C), hypersaline (~35–50 wt % total dissolved solids), metalliferous (Na+Fe+Ca+Cu+Ni+W+
Pb+Zn), multiphase H2O-rich-CO2-NaCl-FeCl2 inclusions (type 4). This inclusion type has not been previously
reported in other Birimian terranes. The composition of the brines, along with carbon isotope data (δ13C of
–14.4 to –4.5‰), suggests a magmatic input to the Gara-style hydrothermal system. The coexistence in the
fluid inclusion assemblages of the magmatic brines with Yalea-style, CO2-rich, metamorphic fluids and the pos-
itive correlation between salinity and homogenization temperatures suggest mineralization was locally con-
trolled by fluid mixing. The interaction of these two chemically contrasting fluids explains the distinctive pet-
rographic characteristics of the Gara-style orebodies. This includes the growth of widespread multi-stage
Fe3+-rich tourmaline (B-rich granite source) and sodic alteration, and ore assemblages consisting of abundant
nickeloan pyrite, (REE)-phosphates, Ni ± Co ± Pb ± Zn minor/trace sulfides, and scheelite. Gold deposition
in the Gara-style hydrothermal system is related to physical and chemical changes of the two fluids during mix-
ing (e.g., decreases in ƒO2 and T in the brines and retrograde boiling of the CO2 component in the metamor-
phic fluids, a “salting out effect”).
Introduction deposits (e.g., Oberthür et al., 1994; Allibone et al., 2002a, b;

MALI is the second leading gold producing country in West Berge, 2011), and gold mineralization throughout Burkina
Africa (after Ghana) and hosts numerous world-class (1–>9 Faso (Klemd and Ott, 1997; Klemd et al., 1997; Beziat et al.,
Moz) Paleoproterozoic gold deposits. Gold mineralization oc- 2008) and eastern and central Côte d’Ivoire (Coulibaly et al.,
curs in two separate areas of the country, both underlain by 2008; Kadio et al., 2010). Birimian rocks of the Kédougou-
rocks of the Birimian Supergroup (2.0-–2.2 Ga) of the West Kéniéba inlier crop out in southwest Mali. This highly gold
African craton (inset Fig. 1). In southern Mali, the Morila, productive/prospective region is known as the west Mali gold
Syama, and Kalana deposits are situated within the Leo-Man belt, and includes the Gara, Yalea, Gounkoto, Sadiola, Yatela,
Shield, which also hosts the well-known Ghanaian gold Tabakoto, and Segala deposits (Fig. 1), plus several exciting
ongoing exploration projects.
† Corresponding author: e-mail, David.Lawrence@randgoldresources.com
The majority of the Malian deposits (and other West African
*Present address: Randgold Resources Ltd, Halkett Street, St Helier, Jer- shear-hosted deposits) can be classified as orogenic gold lodes
sey, Channel Islands, JE2 4WJ. on the basis of their geologic characteristics (cf. Groves et al.,
Submitted: October 22, 2011
0361-0128/13/4090/229-29 229 Accepted: May 12, 2011
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by University of Cape Town user
on 17 September 2023
230 LAWRENCE ET AL.
12°W 6°W 0°
Mako Series
N 14°N
KKI MALI
SENE-
GAL Loulo BURKINA
FASO
Yatela 10°N
Sadiola SIERRA GUINEA Archean
LEONE Birimian
Leo-Man Shield
14° N Post-Birimian
COTE
LIBERIA GHANA
d’IVOIRE
6°N
Ashanti
ATLANTIC
250 125 0 250 km
Kakadian OCEAN
Kenieba
13.5° N 13.5° N
Falé
SM
- mé
Rive
r
SZ
Bab
Sabodala Sitakili
Z
Gara
MT
Bambaraya
L-3
13° N Makana 13° N
Yalea
Segala
Massawa Tabakoto
Gounkoto
Saraya
Bambadji Kenieba
G
am
bi
a
Ri
ve
r
Kedougou
12.5° N
Falémé
R iver
Dialé-Daléma Series Falémé Series Kofi Series
12° W 11.5° W 20 10 0 20 km
Kakadian-Badon batholith- Calc-alkaline, metaluminous Mauritanides Hercynian

ultramafic to felsic rocks TTG plutons belt
Detrital and chemical Towns/villages
Tholeiitic basalts
basin metasedimentary rocks
Orogenic gold deposits (>1 Moz)
Calc-alkaline, peraluminous
Tholeiitic andesites Iron endo- and exo-skarn deposits
granites
Calc-alkaline volcaniclastic SMSZ Senegal-Mali Shear Zone
Neoproterozoic cover
rocks,
sequences MTZ Main Transcurrent Shear Zone
plus volcanic belt-hosted
FIG. 1. Geologic map of the Birimian Kédougou-Kéniéba inlier (KKI), modified after Gueye et al. (2008) and Lawrence
et al. (2013). The dotted line represents the Loulo mining district (Bab = Baboto target, L-3 = Loulo-3 deposit). Inset map
shows the Birimian terranes of the southern half of the West African craton (modified after Feybesse et al., 2006).
0361-0128/98/000/000-00 $6.00 230

FLUID INCLUSION AND STABLE ISOTOPE STUDY AT THE LOULO MINING DISTRICT, MALI 231
1998). However, the composition and origin of the hydro- emplaced at similar times to the TTG intrusive stocks located
thermal fluids responsible for gold mineralization in Mali is along the belts (the Saraya granite shows a U/Pb zircon age of
poorly understood. This fluid inclusion and stable isotope 2079 ± 2 Ma; Hirdes and Davis, 2002).
study addresses this issue and describes the nature of the The Birimian crust of West Africa shows a polycyclic defor-
gold-bearing hydrothermal fluids in the Loulo mining district. mation and metamorphic (greenschist facies) history related
This paper forms the second part of a two-part study at Loulo. to the Eburnean orogenic event at ~2.1 Ga (e.g., Milési et al.,
The first paper (Lawrence et al., 2013) documents the min- 1992; Feybesse et al., 2006). Three deformation phases are
eralogical and geologic characteristics of the various orebod- recorded in the Kédougou-Kéniéba inlier including: a com-
ies within the mining camp. Both studies highlight the role of pressional D1 event related to early thrusting; and two later
multi-fluid sources (metamorphic and magmatic) in the de- transcurrent deformation phases (D2-D3), which led to the
velopment of the Loulo deposits. The interplay of metamor- development of crustal-scale shear zones (Main Transcurrent
phic and magmatic mineralizing fluids has important implica- shear zone and the Senegal-Mali shear zone; Fig. 1) (Ledru et
tions concerning the currently accepted orogenic gold al., 1991; Dabo and Aïfa, 2010, 2011; Lawrence et al., 2013).
paradigm (Groves et al., 1998; 2003; Ridley and Diamond, Transcurrent deformation is synchronous with gold mineral-
2000). ization and the emplacement of the syntectonic, calc-alkaline,
granitoids (Ledru et al., 1989; Pons et al., 1992; Gueye et al.,
Geologic Setting 2008).
Regional geology Mine geology
The Loulo mining district is situated in the eastern part of The geological and structural setting of the Loulo mining
the Senegal-Mali Kédougou-Kéniéba inlier (Fig. 1), which camp is discussed fully in the companion paper (Lawrence et
represents the westernmost Birimian terrane of the West al., 2013), and only the salient features are summarized here.
Africa craton (Fig. 1 inset). The geology of the Kédougou- The Loulo permit is situated approximately 13° N and 11.4°
Kéniéba inlier is comparable to the Birimian granite-green- W, in the semi-arid Kayes region of southwest Mali, 350 km
stone terranes of Ghana (e.g., Leube et al., 1990). As described west of Bamako. The Bambadji-Daléma permits, which rep-
in Lawrence et al. (2013), the inlier consists of two N- to resent the western extension of the Loulo district, are situated
NNE-trending volcano-plutonic belts, known as the Mako on the opposite side of the border in the Kédougou region of
Series and Falémé Series, and two intervening sedimentary eastern Senegal. The Loulo district currently consists of three
basins, referred to as the Dialé-Daléma Series and Kofi Series major deposits (Gara, Yalea and Gounkoto; although the lat-
(Fig. 1). Various generations of granitic rocks intruded both ter is not discussed here), plus numerous satellite deposits
the belts and basins. The inlier is bounded on its western and smaller targets (e.g., Loulo-3, Faraba, Baboto, and P-64),
margin by the Hercynian Mauritanide belt and is uncon- with total gold resources of 15.5 Moz (pub. data from Rand-
formably overlain by flat-lying Neoproterozoic sediments on gold Resources Ltd 2011 annual report). The Loulo orebod-
all other sides. ies, along with other deposits of the west Mali gold belt, are
The volcano-plutonic belts are composed of dominantly structurally controlled by the sinistral, brittle-ductile, Sene-
tholeiitic basaltic and andesitic lavas (mainly the Mako Series), gal-Mali shear zone (Fig. 1). The greatest ore concentration
calc-alkaline volcaniclastic units, and wacke and carbonate occurs in higher order D2-D3 shears, faults, and folds on the
sedimentary rocks (Dia et al., 1997; Diallo, 2001). The Mako eastern wall of the main shear zone (Malian territory), in
volcanic rocks are considered much older than the Falémé metasandstones, carbonaceous calcitic and dolomitic mar-
belt, dated between 2160 and 2200 Ma (Boher, 1991; Dia et bles, and hydrothermal-tectonic breccias of the Kofi Series
al., 1997). The western side of the Mako belt is intruded by a (Fig. 2). The Falémé Series, to the west of the Senegal-Mali
complex suite of pre- and syntectonic ultramafic to felsic shear (Senegalese territory), is marked by low-grade gold
rocks of the Badon-Kakadian batholith (e.g., Dioh et al., 2006; mineralization and magnetite-bearing endo- and exoskarn de-
Gueye et al., 2008). This batholith is dated in the age range of posits of the Falémé iron ore district (Schwartz and Melcher,
2080 to 2210 Ma (Dia, 1988; Dia et al., 1997; Gueye et al., 2004). These iron-oxide associated deposits are related to
2007). The Mako belt, as well as the Falémé Series, is also in- highly Na altered (albitization of plagioclase) granodiorites,
truded by syntectonic (2070–2080 Ma) calc-alkaline, I-type, tonalities, and microdiorites. In places, these altered rocks are
hornblende-biotite-bearing tonalite-trondhjemite-granodior- now best described as albitites.
ite (TTG) granitoids (Hirdes and Davis, 2002; Gueye et al.,
2008). Geochemical studies carried out on both the Mako and Economic geology
Falémé volcanic-intrusive rocks indicate arc-related affinities Lawrence et al. (2013) describe in detail the mineralization
(Schwartz and Melcher, 2004; Dioh et al., 2006; Pawlig et al., characteristics of the Loulo mining camp. Geologic and pet-
2006). rographic studies highlight the significant differences be-
The intervening sedimentary basins are composed of thick tween the main Gara and Yalea deposits. These orebodies are
sequences of younger marine argillites, quartz-, lithic- and the main focus of this fluid inclusion and stable isotope study.
feldspar-bearing wackes, calc-alkaline volcaniclastic rocks, The Gara deposit is a carbonate-quartz stockwork style ore-
and platform carbonates that are intruded by peraluminous, body confined to a folded unit of strongly tourmalinized
S-type granites (Bassot, 1987; Hirdes and Davis, 2002). The quartzwacke (5-–20 m thick) over a strike length of 1.2 km
siliciclastic fraction is probably the erosional product of the is- (Fig. 2A). The Gara stockwork consists of three main vein
land arcs (Lawrence, 2010). The peraluminous granites were generations. Type I veins and veinlets are ankerite-rich-milky
0361-0128/98/000/000-00 $6.00 231

232 LAWRENCE ET AL.
(A) Gara (B) Yalea NNE-trending, 2nd-

order, sinistral, D2 shear,
following a P-shear
geometry with respect to
Surface outcrop the SMSZ
P-125 satellite
of the tourmaline- - situated along a
rich ore zone N-S chloritized
shear Yalea North lode
The geometry - hosted in albite-tourm-
of the folds is aline altered breccias
controlled by
transpressional
movement along
a series of D2
NNE-trending Yalea Main ore body
D2 folds with axial trends Yalea Main-
2nd-order shears - situated along a N-S
to the NNE and plunge SSW Central Zone
dilational R-shear formed
at 10-30º dip
from reactivation of the
NNE shears during D3
Pit outline transtension
Late dextral
E-W fault
Synform
Yalea Main-
Short left-hand displacements
Southern
between a series of NNE-
Pit outline Zone
Antiform trending shears
N N
100 0 100 m 200 0 200 m
FIG. 2. Plan maps showing the structural setting of the Gara (A) and Yalea (B) deposits (modified from Lawrence et al.,
2013). Solid red lines = D2-D3 shears; dashed red lines = inferred D2-D3 shears. SMSZ = Senegal-Mali shear zone.
quartz-pyrite veins, which have been reactivated by type II Both mineralization styles show similar ore mineralogy and
gray quartz-pyrite veins. Both vein generations are gold-bear- thus are interpreted to have formed contemporaneously. A
ing and formed during D3 transtensional deformation (exten- barren quartz-calcite vein stage is also observed in the wall
sional shear veins). Type III veins are late, barren, quartz-rich rocks, postdating mineralization and all stages of alteration.
calcite veins, which crosscut the gold-bearing veins and asso- In contrast to Gara, the Yalea Main orebody is associated
ciated alteration. with As-rich ore assemblages (~50:50 arsenopyrite/pyrite
Type I and II vein generations show a similar ore paragen- ratio), and shows a distinct lack of base metal sulfides, (REE)-
esis. The main characteristics include the following: sulfide phosphates, and scheelite. Paragenetic studies reveal a multi-
assemblages predominated by pyrite (>99% of sulfide popu- stage gold development comprising of early arsenian pyrite
lation); abundant (REE)-phosphates (apatite, monazite, and and minor arsenopyrite (ore stage 1); a second generation of
rarer xenotime) and tungstates (scheelite), accounting up to arsenopyrite growth (ore stage 2); and, lastly, a minor phase of
5% of the total ore minerals; and trace sulfides consisting of Cu sulfide growth consisting of tennantite, chalcopyrite, and
Ni-bearing phases (e.g., gersdorffite and pentlandite). Gold is Cu-bearing pyrite (ore stage 3). Hydrothermal alteration
temporally associated with pyrite as inclusions, with some linked to the Yalea Main orebody is tourmaline absent and
local remobilization into microfractures crosscutting the sul- associated with an early (pre-ore) ankerite-albite-silica stage
fide grains. The alteration halo associated with the gold-bear- and a synmineralization sericite-chlorite stage.
ing veins is distinguished by widespread, multistage tourma- Lawrence et al. (2013) show that mineralization elsewhere
linization and pink albitization. in the Loulo district is distinguished by either Gara- or Yalea
The Yalea deposit is situated 6 km to the southeast of Gara (Main)-style characteristics. A selection of these satellite ore-
and lies along a third-order Riedel shear that strikes N-S over bodies and minor targets were also chosen for the fluid inclu-
2 km (Fig. 2B). This structure formed during D3 deformation sion investigation (Yalea North, Loulo-3, and Baboto). The
along a NNE-trending second-order D2 shear, which hosts Yalea North ore shoot is hosted in tourmaline-bearing brec-
mineralization farther to the north at Loulo-3 and Baboto. cias to the north of Yalea Main, with ore and alteration fea-
The Yalea complex consists of one main orebody (Yalea Main; tures analogous to Gara. The Loulo-3 and Baboto quartz vein
focus of this study) and several satellite lodes (Yalea North and disseminated lodes are classified as Yalea-style deposits
and P-125). Auriferous sulfides at Yalea Main are located along and are situated to the north of the Yalea complex. The loca-
narrow shear bands within highly altered rock. Sulfides largely tions of the studied orebodies are shown in Figure 1 and the
occur as disseminations, although quartz-pyrite-arsenopyrite general characteristics (size, grade, mineralization styles, and
± ankerite veinlets are seen occasionally filling the shears. host rock lithology) are summarized in Table 1.
0361-0128/98/000/000-00 $6.00 232

TABLE 1. General Characteristics of the Loulo Gold Deposits and Descriptions of Samples Used in the Fluid Inclusion and Stable Isotope Studies
Fluid inclusion study Stable isotope study
Deposit/ Min. Resource Grade Sample Sample Major Minor No. Sample Measured No.

target style (Moz) (g/t) Host rock Alteration description no. FI types FI types D description Sample no. isotopes D
Gara-style orebodies
Gara VH 3.1 4.0 Tourmaline- Tourmaline- Milky quartz- PT-5a, -6, 1-e, 3-e, 1-l, 2-l 924 Milky quartz- PT-5a, -6, -8, -9, δ18Oqtz, δ18Ocarb, 34
rich albite ankerite pyrite -8, G-10 4-e ankerite pyrite LD-13, -20, -28, -30, δ13C, δ34S
quartzwackes (type I) veins LD-28, -32, (type I) veins -31, -32, -38, -41,
0361-0128/98/000/000-00 $6.00
-41, -45 -44, -45, -46, G-7
Late gray G-4, -5, 1-e, 3-e, — 207 Late gray G-5, LD-27, δ18Oqtz, δ34S 4
quartz-pyrite LD-27 4-e quartz-pyrite -51, -53
(type II) veins (type II) veins
Yalea BH Included in Yalea Hydrothermal- Tourmaline- Quartz-ankerite- PT-29, -30, 1-e, 4-e 3-e 126 — — — —
North Main resource tectonic albite pyrite veins 07YD-11
breccias
Yalea-style orebodies
Yalea DH 6.3 4.9 Calcareous Ankerite- Central zone: PT-26, 1-e, 2-e 1-l, 2-l 325 Central zone: PT-18, -20, δ34S 6
Main graywackes quartz-albite- quartz-pyrite- 08YD-10, 3-e pyrite-arseno- 07YD-65
chlorite- arsenopyrite 07YD-17-18, pyrite stringers
sericite veins -60 and massive sulfides
Southern zone: 08YD-24, 1-e 1-l 149 Central zone: PT-26, 07YD-17, δ18Oqtz, δ18Ocarb, 12
quartz-pyrite- -29, -30 quartz-ankerite- -18, -60, -69, δ13C, δ34S
arsenopyrite pyrite veins 08YD-10
veins Southern zone: 08YD-29, -30 δ18Oqtz 2
233
quartz veins
Southern zone: 07YD-71, δ18Oalb, δ18Ocarb, 11
albite-ankerite -76, -80,
alteration with 08YD-24, δ13C, δ34S
disseminated -31, -33
sulfides
Loulo-3 VH 0.3 3.5 Graywackes Chlorite- Quartz-pyrite- L3-5 1-e, 2-e 3-e 75 — — —
sericite arseopyrite veins
Baboto DH 0.3 2.2 Graywackes Silica-albite Quartz-pyrite- BAB-2, 1-e, 2-e — 136 — — — —
and breccias arseno-pyrite -3, -10
veins
Non-mineralized/ unaltered rocks

Gara — — — Wackes & — Barren quartz- PT-5b, 1-e, 2-e, 1-l 342 Barren quartz- G-39, -40, LD-11 δ18Oqtz, δ18Ocarb, 6
marbles calcite G-39, 3-e calcite (type III) δ13C
(type III) veins LD-11 veins
Kofi calcitic marbles G-13, LD-16, -26 δ18Ocarb, δ13C 6
FLUID INCLUSION AND STABLE ISOTOPE STUDY AT THE LOULO MINING DISTRICT, MALI
Yalea — — — Wackes, — Barren quartz- PT-21, -23 1-e, 2-e, 1-l 287 Barren quartz- 07YD-90 δ18Oqtz, δ18Ocarb, 3
Main arkoses calcite veins 3-e calcite veins δ13C
and marbles Kofi dolomitic 07YD-52, -53, -89 δ18Ocarb, δ13C, 6
marbles with δ34S
syngenetic pyrite
Notes: Mineralization (Min.) styles: BH = breccia-hosted deposit; DH = disseminated-hosted mineralization (BH and DH deposits also contain minor veining for fluid inclusion and O-C isotope
analysis); VH = quartz-carbonate vein-hosted deposit; fluid inclusion types: 1-e and 1-l = early and late CO2-(N2)-(CH4) inclusions, respectively; 2-e and 2-l = early and late H2O-NaCl inclusions, re-
spectively; 3-e = early H2O-CO2-NaCl inclusions; 4-e = early multiphase H2O-CO2-NaCl-FeCl2 inclusions; δ18Oqtz, δ18Oalb, δ18Ocarb = measured δ18O for quartz, albite, and carbonate, respectively;
No. D = number of microthermometric and isotope data measurements
233

234 LAWRENCE ET AL.
Sampling and Methodology computer software package (Bakker, 2003). Fluid composi-
tions (e.g., salinity, densities, and molar fractions) were deter-
Sampling mined using the BULK program, whereas the ISOC program
This fluid inclusion and stable isotope study is the first of its was used for isochore projections. The following equations of
kind in western Mali. Twenty-four mineralized (>5 g/t Au) state were used: Zhang and Frantz (1987) for inclusions in the
and nonmineralized (<0.1 g/t Au) quartz vein samples were H2O-NaCl system; and Bowers and Helgeson (1983) and
analyzed from Gara and Yalea Main as part of the fluid inclu- Bakker (1999) for CO2-(N2)-(CH4)-(H2O) inclusions.
sion investigation. At Gara, all quartz generations representa- The identification of daughter and associated minerals
tive of the vein stockwork paragenesis were examined (gold- within the fluid inclusions was carried out using transmitted
bearing type I and II veins; and late, barren type III veins). At light microscopy and scanning electron microprobe analysis
Yalea Main, both quartz-sulfide veinlets associated with the of open inclusions (cf. Campbell et al., 2001). The latter tech-
mineralized shearing event and the late nonmineralized veins nique was especially useful in cases where the solid phases
were studied. In addition, fluid inclusions from seven samples were too small to observe (<1 μm). Secondary electron and
of auriferous quartz veining from the minor targets (Yalea backscattered electron imaging (gold- and carbon-coated
North, Loulo-3, and Baboto) were also investigated. samples) of daughter and associated minerals were carried
The stable isotope (δ18O, δ13C, and δ34S) study concen- out using a Zeiss EVO 50 electron microscope at Kingston
trated on the Gara and Yalea Main deposits. A total of 47 University. Semiquantitative analyses of the solid phases were
samples were chosen for analysis which included the follow- determined using an Oxford Instruments X-ACT energy dis-
ing: (1) gold-bearing quartz-ankerite-sulfide veins and vein- persive spectrometer (EDS). Raman spectra for daughter
lets, (2) Yalea Main disseminated auriferous sulfides (repre- minerals were difficult to acquire and interpret due to their
sentative of ore stage 1 and 2), (3) pre-ore albite-carbonate small size.
wall-rock alteration, (4) barren (<0.1 g/t Au) quartz-calcite
veins (postdate alteration and mineralization), (5) sedimen- Stable isotopes
tary/diagenetic pyrites from unaltered host sedimentary Minerals were separated by crushing, sieving and hand-
rocks, and (6) carbonate mineral separates from unaltered picking down to a 250 μm fraction. Approximately 5 to 10 mg
calcitic and dolomitic marble wall rocks. Descriptions of the of sulfides were separated for sulfur analysis, whereas 2 to 5
samples used in the fluid inclusion and isotope investigations mg of silicates and carbonates were utilized for carbon and
are summarized in Table 1. oxygen isotopes. The purity of each sulfide sample was greater
than 80% (in most cases >90%), whereas silicate and carbon-
Fluid inclusions ate separates were almost totally pure. Stable isotope analysis
Petrographic, microthermometric, and laser Raman spec- was carried out at the Scottish Universities Environmental
troscopic studies of fluid inclusions were carried out at Kingston Research Centre (SUERC) at East Kilbride, Glasgow. Silicate
University London. Quartz samples were prepared as doubly separates were analyzed using a laser fluorination procedure
polished wafers with a thickness of 150 μm. Microthermom- (Sharp, 1990), with laboratory reproducibility better than ±
etry experiments were carried out using a Linkam LMS600 0.3‰ (1σ). Carbonate and sulfide samples were analyzed by
heating-freezing stage attached to a Nikon Optiphot micro- standard techniques (Craig, 1957; Robinson and Kusakabe,
scope. The stage was regularly calibrated using FLINCOR 1975), with reproducibility’s of ± 0.1‰ for δ13C, ± 0.2‰ for
synthetic standards of pure CO2 (triple point of –56.6°C) and δ18O, and ± 0.2‰ for δ34S (1σ). Oxygen, carbon, and sulfur
H2O (critical point of 372.4°C; melting temperature at isotopes are reported in standard notation as per mil (‰) de-
–0.2°C) fluid inclusions. Heating rates of 1°C/min were em- viations from the Vienna Standard Mean Ocean Water (V-
ployed for measurements below 30°C and 5°C/min up to SMOW), Vienna PeeDee Belemnite (V-PDB), and Vienna
400°C. Consequently, the accuracy of the measurements was Cañon Diablo Troilite (V-CDT) standards, respectively.
approximately ± 0.2ºC during the freezing cycle and ± 2ºC
during heating measurements. Fluid Inclusion Petrography
Raman analyses of fluid inclusions were undertaken using a
Renishaw RM1000 Raman spectrometer attached to an Olym- Timing
pus BH-2 microscope. A neon ion laser (633 nm) was used, Transmitted light petrography of mineralized and nonmin-
with a source power of 500 mW and a focused spot size of ~5 eralized quartz veins at Loulo show variable degrees of re-
μm. The Raman was calibrated using a silicon standard. Data crystallization. The most recrystallized, deformed, and strained
manipulation was carried out using the Grams32 software quartz occur along discrete zones and exhibit diagnostic fea-
package, with a running time of between 30 to 60 seconds. tures such as polycrystalline, undulose, stylolitic, and triple-
The molar compositions of the fluid inclusions were calcu- point textures. Limited work was carried out on these samples
lated using peak area measurements of the Raman spectrum as the inclusions commonly show evidence of reequilibration
and relative Raman cross section values given by Burke and, in mineralized veins, are unlikely to represent the origi-
(2001), i.e., 2.7 for CO2, 1.0 for N2, and 7.2 for CH4. The in- nal gold-bearing fluid. Between these areas of high strain, the
strument efficiency was calculated at 0.65. Peak positions for quartz veins are relatively undeformed, as revealed by scan-
CO2 (twinned peaks), N2 and CH4 occur at ~1282 cm–1 (v1) ning electron microscope-cathodoluminescence studies (SEM-
and ~1386 cm–1 (v2), 2330 cm–1 and 2913 cm–1, respectively. CL), which indicate recrystallized zones are largely concen-
The P-T-V-X state of the fluids was calculated from micro- trated along grain boundaries. The majority of fluid inclusions
thermometric and Raman data using the FLUIDS (version 1) in quartz cores are interpreted to be primary in origin (termed
0361-0128/98/000/000-00 $6.00 234

“early” inclusions here). In all studied samples, early inclu- or total leakage of selective components (i.e., tips at inclusion
sions form two groups of fluid inclusion assemblages: along edges; fractures aligned along inclusion walls). Where possi-
growth zones associated with primary quartz growth (Fig. 3A) ble, inclusions suspected of being modified postentrapment
or as random clusters within the cores of the host grains. In were not measured. The occurrences of early and late fluid
mineralized zones, the analyzed quartz is temporally linked to inclusions in the various quartz generations, as well as de-
sulfide and gold formation suggesting the early inclusions are scriptions of the different inclusion types present, are dis-
representative of the auriferous fluid(s). cussed in detail in the following section.
Secondary inclusions (termed “late” inclusions here) are
also observed and generally follow healed microfractures Fluid inclusion types and occurrence
(Fig. 3B), which commonly crosscut quartz grain boundaries Based on the petrographic and compositional features of fluid
(transgranular trails). Late submicrometer inclusions are also inclusions at room temperature and their Raman characteris-
seen as zones along recrystallized grain boundaries (inclu- tics, four types of inclusions are recognized in the various quartz
sions too small to measure). Some fluid inclusions showed generations at Loulo—type 1: CO2 ± N2 ± CH4 inclusions, type
evidence at room temperature for necking down and partial 2: H2O-NaCl inclusions, type 3: H2O-CO2-NaCl ± N2 ± CH4
A B
Trail of
type 1-l
100 μm 40 μm
C D
Type 4-e
D
Type 2-e
Type 3-e
Type 1-e
Type 3-e
20 μm 15 μm
E F
Type 1-e
Cluster of type 1-e
15 μm 20 μm
FIG. 3. Photomicrographs (taken at room temperature) of fluid inclusions present in mineralized quartz at Gara and Yalea
Main. A) Quartz crystal zonation at Yalea Main, defined by mineral inclusions (sulfide and other gangue phases) and fluid in-
clusions (early inclusions). Opaque acicular crystals on the left of the image are arsenopyrites. B) Late, small (<5 μm), type-
l-l inclusions along sealed microfracture planes in type I quartz vein at Gara. C) An early fluid inclusion assemblage at Yalea
Main, showing the coeval entrapment of type 1-e and 2-e inclusions. D) An early fluid inclusion assemblage at Gara, show-
ing the coexistence of type 3-e and 4-e inclusions. E) A cluster of type 1-e inclusion at Gara (similar inclusions are also seen
at Yalea Main). F) to J) Higher magnitude images of the four different types of early inclusions. Type 1-e and 1-l = early and
late CO2 ± N2 ± CH4 inclusions, respectively; type 2-e = early H2O-NaCl inclusions; type 3-e = early H2O-CO2-NaCl inclu-
sions; type 4-e = early, multiphase, H2O-CO2-NaCl-FeCl2 inclusions. L = liquid phase, V = vapor phase.
0361-0128/98/000/000-00 $6.00 235

236 LAWRENCE ET AL.
G H
LCO2
Type 2-e
Type 3-e
Type 2-e LH2O

20 μm 15 μm
I J
Type 4-e Type 4-e
LCO2
Halite
LH2O Halite
Fe-
chloride
LCO2
Fe-chloride Unknown
LH2O
5 μm 5 μm
FIG. 3. (Cont.)
inclusions, and type 4: multiphase H2O-CO2-NaCl-FeCl2 ± veins, type 1-e inclusions are temporally related to type 2-e
CH4 ± N2 inclusions. Such an array of inclusion types (types and 3-e inclusions (Fig. 4B). Late type 1 inclusions are seen
1, 2, and 3) are common fluid inclusion assemblages in Bir- along microfractures in mineralized and nonmineralized
imian orogenic gold deposits (Schwartz et al., 1992; Klemd quartz samples at Gara and Yalea Main (Figs. 3B, 4).
and Ott, 1997; Klemd et al., 1997; Schmidt Mumm et al., Type 2: Rounded two-phase aqueous inclusions (5–30 μm
1997; Yao et al., 2001; Willie and Klemd, 2004; Coulibaly et diam) are easily distinguished from the carbonic inclusions by
al., 2008). However, Loulo also shows a remarkable concen- their transparency and low-relief boundaries (Fig. 3C, G).
tration of hypersaline, multiphase, H2O-CO2-NaCl-FeCl2 in- Vapor volumetric proportions (VH2O) at 20° to 25°C are typi-
clusions (type 4). Similar inclusions have only been reported cally less than 20%, and no carbonic phase was detected in
elsewhere in the Birimian crust at the Morila deposit in these inclusions. The H2O-NaCl inclusions occur in both
southern Mali (Hammond et al., 2011). The distribution of early (2-e) and late (2-l) fluid inclusion assemblages (Fig. 4),
the four inclusion types observed in the Loulo quartz samples similar to type 1 inclusions. Type 2-e inclusions are confined
vary among deposit styles and between mineralized and non- to barren veins (3–51% of the inclusion population per
mineralized veins. The nature and mode of occurrence of sample) and mineralized samples in the Yalea-style deposits
these inclusions are outlined below, and illustrated in Figures (mainly 15–35%) (absent from the Gara-style orebodies).
3 and 4. The fluid inclusion populations observed in the stud- Minor type 2-l inclusions (<5% of inclusion population) occur
ied deposits are graphically shown in Figure 5. along inclusion trails with more abundant type 1-l inclusions
Type 1: Volatile-rich inclusions occur as early (1-e) and late in gold-bearing samples at Gara (type I veins) and Yalea Main.
(1-l) mono- or two-phase inclusions at room temperature, Type 2-l inclusions in these deposits are also seen as isolated
with no visible aqueous phase detected during microthermo- inclusions or in clusters away from other inclusion types, dis-
metric experiments. Type 1 inclusions are between 5 and 35 tinguished by their low homogenization temperatures in com-
μm in size, and contain rounded to irregular shaped habits parison to type 2-e inclusions in more multiphase aggregates.
and dark, high-relief rims (Fig. 3C, E, and F). CO2-rich in- Type 3: H2O-CO2-NaCl ± N2 ± CH4 inclusions occur as
clusions are the most dominant inclusion type at Loulo, seen two- or three-phase inclusions at room temperature, with a
in all gold-bearing quartz samples (generally >70% of the in- size range from 5 to 20 μm (Fig. 3D, H). Mixed aqueous-car-
clusion population). Barren veins also contain abundant type bonic inclusions are the least abundant inclusion type at
1 inclusions, but in slightly lower abundances between 40 and Loulo, confined to early fluid inclusion assemblages (Fig. 4).
75%. Type 1-e inclusions, developed along planar growth They are, however, seen at both Gara- and Yalea-style deposits
zones or in randomly distributed groups, occur with other in- (mainly ≤10% of inclusion population), and more commonly
clusion types (Figs. 3C, 4) or form clusters on their own (Fig. in the barren vein samples (7–42%). Aggregates of type 3 in-
3E). In auriferous samples from the Gara-style orebodies, the clusions within auriferous veins characteristically show vari-
coexistence of type 1-e, 3-e, and 4-e inclusions are clearly seen able CO2 volumetric proportions (VCO2) between 10 and 90%,
(Fig. 4A). In the Yalea-style deposits and all studied barren whereas inclusions in barren quartz generally exhibit more
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A Gara B Yalea Main

Cluster of
Transgranular trail of type 1-l
type 1-e incs
and rare type 2-l incs Transgranular trail of type 1-l
and rare type 2-l incs
Cluster of
type 1-e incs
Quartz
grain boundary
Isolated
type 2-l inc
Type 1-e, type 2-e and

rare type 3-e incs following
crystal zonation
Cluster of type 1-e,
Type 1-e, type 3-e and
type 2-e and rare
type 4-e incs following Cluster of type 2-l incs type 3-e incs
crystal zonation
Isolated
Early (-e) and late (-l) mono- type 2-l inc
phase CO2-(N2)-(CH4) type 1
incs
Extremely small (<1µm) type Early (-e) and late (-l) bi-phase
1-l incs along re-crystallized type 1 incs
grain boundary Early (-e) and late (-l) H2O-
NaCl type 2 incs Quartz
Early (-e) bi-phase H2O-CO2 grain
-NaCl type 3 incs boundary
Cluster of type 1-e, Early (-e) 3-phase type 3 incs
type 3-e and type
Cluster of
25 µm 4-e incs Early (-e) multi-phase H2O- 30 µm type 2-l incs
CO2-NaCl-FeCl2 type 4 incs
Fig. 4. Schematic maps showing the distribution (at room temperature) of the main fluid inclusion types in mineralized
quartz veins at Gara (A) and Yalea Main (B); incs = inclusions.
uniform compositions (VCO2 20–35%). At the Gara-style ore- quartz samples analyzed in this study. Type 4-e inclusions are
bodies, type 3-e inclusions are commonly associated with co- characteristically small (<10 μm), with the gaseous phase typ-
eval type 4-e inclusions (Fig. 3D). ically less than 20 vol % at room temperature. Optical studies
Type 4: Hypersaline, multiphase, H2O-CO2-NaCl-FeCl2 ± show these inclusions contain one to four visible daughter
CH4 ± N2 inclusions (Fig. 3D, I, J) are common in gold-bear- and/or captive minerals (5–35 vol %).
ing samples at Gara (type I and II veins) and Yalea North
(3–67% of the inclusion population; mainly 5–20%) (Figs. 4, Identification of solid phases
5). However, this inclusion type is notably absent from other Type 4-e fluid inclusions contain numerous solid phases and
can be considered as a complex multi-salt solution. The com-
Type 1 Type 2 Type 3 Type 4 mon appearance and relative proportions of the solids suggest
100
that most are true daughter minerals (cf. Goldstein, 2003).
Halite is the most dominant daughter phase and occurs as
small (<3 μm), moderate relief, cubic crystals (Figs. 3I, J, 6A,
Fluid Inclusion Population (%)
80 B). Iron chlorides are also observed as green, high birefrigent,

prismatic crystals (Figs. 3I, J, 6C). They either represent
60 lawrencite (FeCl2) or iron-chloride-potassium hydrates
(Shepherd et al., 1985; Kwak et al., 1986). Other daughter
minerals were too small (<1 μm) to identify optically.
40
Electron microprobe analysis of open inclusions reveals the
minor presence of other chloride phases in and around the in-
20 clusions, including sylvite (KCl) and Ca-bearing chlorides.
Anhedral carbonate minerals (ankerite and calcite) and iron-
0 oxides are also observed (Fig. 6B-D). Hematite and mag-
GA YN YM BAB L3 BV netite are detected in separate inclusions (the latter distin-
Ore body/ barren veins guished from the former by its octahedral habit). Mounds of
FIG. 5. Fluid inclusion populations in the Loulo mining district, from the halite (Fig. 6E) and extremely rare sylvite crystals are also seen
analysis of 31 mineralized and nonmineralized quartz veins. Percentages es- along quartz fracture surfaces, and represent the dissolved
timated at room temperature via point counting over random fields of view components of type 4 inclusions (precipitated after inclusion
(at least 10 per sample). Gara-style deposits = Gara (GA) and Yalea North opening). Electron microprobe imaging also documents the
(YN); Yalea-style deposits = Yalea Main (YM), Baboto (BAB), and Loulo-3
(L3); BV = barren veins from Gara and Yalea Main; type 1 = CO2-(N2)-(CH4) existence of solid halite crystals that appear to be intergrown
inclusions; type 2 = H2O-NaCl inclusions; type 3 = H2O-CO2-NaCl inclu- with the host quartz (no evidence of an inclusion cavity) (Fig.
sions; type 4 = multiphase H2O-CO2-NaCl-FeCl2 inclusions. 6F). Broad beam energy dispersive spectrometric (EDS)
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238 LAWRENCE ET AL.
A B
Halite
Hematite
Carbonates
Halite
1 μm 1 μm
C D
Magnetite
Carbonates
B Hematite
Fe- chloride K mica

600 nm 1 μm
20μm
E F
Halite
Halite
2 μm 2 μm
FIG. 6. Secondary electron microprobe (SEM) images of opened, quartz-hosted, multi-phase H2O-CO2-NaCl-FeCl2 type
4-e inclusions from Gara and Yalea North. A) to D) Images of the various mineral phases observed in open inclusion cavi-
ties. E) Quartz fracture surface showing mounds of halite precipitated out of solution during inclusion opening. F) Halite in-
tergrown with quartz (no evidence of a fluid inclusion cavity). Samples were gold-coated to obtain high resolution.
analyses of chloride phases in opened inclusions identified presented in Tables 3 to 6, and the results are plotted in Fig-
the presence of Cu+Ni+W±Sr±Ba±Pb±Zn, indicating a high ures 7 to 11. The data collected from the various inclusion
metal content for this fluid type. The concentrations of these types, from mineralized and nonmineralized veins, are men-
elements are not well quantified due to geometry of the un- tioned separately in the following sections.
even fracture surfaces, but levels >2,000 ppm are suggested
based on the lower limits of detection of the energy dispersive Gold-bearing quartz
spectrometer. In a few cases, Cu, Ni, and W concentrate at the Type 1 inclusions: CO2 ± N2 ± CH4 inclusions are gas-only
apex of chloride crystals. Lastly, muscovite and extremely rare (no water detected by clathrate melting). The melting tem-
barite are also observed as solid phases in type 4-e inclusions. perature of CO2 (Tm(CO2)) varies throughout the Loulo district.
These two minerals are assumed to be accidently trapped This implies variable concentrations of N2 and/or CH4 within
solids because of their irregular appearance and inconsistent this inclusion type. In the first stage of auriferous veining at
sizes relative to the inclusion cavity. Gara, type 1-e inclusions generally contain a narrow Tm(CO2)
range from –58.5° to –56.6°C, with a majority of inclusions
Microthermometry showing melting temperatures close to the CO2 critical point
A summary of the microthermometric data measured from of –56.6°C (i.e., near-pure CO2 compositions) (Fig. 7A). Similar
fluid inclusions at the Gara-style (Gara and Yalea North) and measurements are recorded from gold-bearing samples at Yalea
Yalea-style (Yalea Main, Loulo-3, and Baboto) deposits is North. Type 1-e inclusions measured from the second gener-
shown in Table 2. The full dataset for individual deposits is ation of mineralized veining at Gara display more variable
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TABLE 2. Summary of Petrographic, Microthermometric and Raman Data of Fluid Inclusions in Gold-Bearing Quartz Veins from
the Loulo Mining District
Inclusion type System Occurrence Microthermometric and Raman data
Type 1-e
CO2-(N2)-(CH4) Gara-style: Tm(CO2): –75.0° to –56.6°C (mainly between –57.0° and –56.6°C);
Th(CO2)(L): –53.5° to 31.0°C (majority between –10.0° and 30.0°C); ρtot: 0.513 to
1.168 g/cm3; CO2-N2-CH4*: 58.3 to 100; 0° to 18.5; 0 to 32.7 mol %, respectively
(mean values: 92.0-3.8-4.2 mol %)
Yalea-style: Tm(CO2): –65.7° to –56.7°C; Th(CO2)(L): –14.3° to 29.3°C; ρtot: 0.671 to

0.843 g/cm3; CO2-N2-CH4*: 49.1 to 95.7; 4.3 to 45.7; 0 to 28.2 mol %, respec-
tively (mean values: 82.7-13.1-4.2 mol %)
Type 1-l CO2-(N2)-(CH4) Gara-style: Tm(CO2): –57.4° to –56.6°C; Th(CO2)(L): –0.1° to 25.3°C; ρtot: 0.707 to
0.929 g/cm3
Yalea-style: Tm(CO2): –57.9° to –56.9°C; Th(CO2)(L): 9.1° to 28.1°C; ρtot: 0.654 to

0.781 g/cm3
Type 2-e H2O-NaCl Yalea-style: Te: –24.9° to –21.0°C; Tm(ice): –8.9° to –0.4°C; Th(L): 176° to 350°C;
Td: 250–320°C; salinity: 0.7 to 12.7 wt % NaCl equiv; ρtot: 0.606 to 0.980 g/cm3;
XH2O: 0.957 to 0.998
Type 2-l H2O-NaCl-(FeCl2) Gara-style: Te: –38.8º to –25.9ºC; Tm(ice): –20.4º to –9.6ºC; Th(L): 140º to 197ºC;
salinity: 13.5 to 22.6 wt % NaCl equiv; ρtot: 0.935 to 1.066 g/cm3; XH2O: 0.917 to
0.987
Yalea-style: Te: –29.9° to –21.2°C; Tm(ice): –20.7° to –14.0°C; Th(L): 176° to

247°C; salinity: 17.8 to 22.8 wt % NaCl equiv; ρtot: 0.937 to 1.041 g/cm3; XH2O:
0.916 to 0.938
Type 3-e H2O-CO2-NaCl Gara-style: Tm(CO2): –96.0° to –56.6°C (mainly between –57.0° to –56.6°C);
Tm(cl): –6.0° to 7.9°C; Th(CO2)(L): –15.8° to 30.0°C; Th(L): 251° to 351°C; Th(V): 261°
to 334°C; Td: 200° to 328°C; salinity: 4.1 to 21.3 wt % NaCl equiv; ρCO2: 0.596 to
1.013 g/cm3; ρtot: 0.676 to 1.010 g/cm3; XCO2: 0.028 to 0.667; CO2-N2-CH4*: 57.0
to 100; 0 to 15.5; 1 to 27.6 mol %, respectively (mean values: 90.7-3.1-6.2 mol %)
Yalea-style: Tm(CO2): –58.5° to –57.0°C; Tm(cl): 4.2° to 9.0°C; Th(CO2)(L): 3.4° to

26.2°C; Th(L): 243° to 309°C; Th(V): 279° to 284°C; Td: 247° to 284°C; salinity: 2.0
to 10.2 wt % NaCl equiv; ρCO2: 0.689 to 0.831 g/cm3; ρtot: 0.798 to 0.996 g/cm3;
XCO2: 0.070 to 0.757; CO2-N2-CH4*: 79.9 to 96.8; 3.2 to 20.1; 0 mol %, respec-
tively (mean values: 89.1-10.9-0 mol %)
Type 4-e Multiphase Gara-style: Tm(CO2): –62.8° to –56.6°C (mainly between –57.6° to –56.6°C);
H2O-CO2-NaCl-FeCl2 Th(CO2)(L): 4.1° to 28.1°C; Ts: 283° to 372°C; Td: 250° to 380°C; salinity1: 36.9 to
44.5 wt % NaCl equiv; salinity2: 37.2 to 62.6 wt % NaCl equiv; ρCO2: 0.654 to
0.903 g/cm3; ρtot: 1.235 to 1.513 g/cm3; XCO2: 0.017 to 0.104
Notes: e and l = early and late inclusions, respectively; Tm(CO2) = melting temperature of CO2 phase; Te = eutectic melting temperature; Tm(ice) = final ice
melting temperature; Tm(cl) = clathrate melting temperature; Th(CO2)(L) = homogenization temperature (to the liquid phase) of CO2 phase; Ts = dissolution tem-
perature of halite; Th(L) = final homogenization temperature (to the liquid phase); Th(V) = final homogenization temperature (to the vapor phase); Td = de-
crepitation temperature; ρCO2 = density of CO2-rich phase; ρtot = bulk density; XH2O and XCO2 = mole fractions of H2O and CO2 (incl. N2 and CH4), respec-
tively; CO2-N2-CH4* = molar compositions of the gaseous phase determined by Raman analysis; for type 4 inclusion, salinity1 = salinities calculated from Ts
and salinity2 = salinities calculated from volumetric proportions of different phases (using equations of Shepherd et al., 1985); densities calculated using mi-
crothermomteric and Raman data
Tm(CO2) between –75.0° and –56.6°C, indicating the presence of type 1-e inclusions homogenize into the liquid phase
of additional gas species. In contrast, type 1 inclusions from (Th(CO2)(L)) from –10.0° and 25.0°C (Fig. 7B). Estimated bulk
auriferous samples representative of the Yalea-style mineral- densities (ρtot), based on Th(CO2) and Raman data, differ be-
ization always contain depressed CO2 melting temperatures tween the Gara-style deposits (0.513 to 1.168 g/cm3) and the
between –65.7° and –57.0°C (Fig. 7A), with the lowest tem- Yalea-style deposits (0.671 to 0.843 g/cm3). Type 1-l inclu-
peratures measured from Baboto and the southern zone of sions, which are found at Yalea Main and the first vein gener-
the Yalea Main deposit (samples 08YD-24, 08YD-29, and ation at Gara, show no systematic microthermometric differ-
08YD-30). ences to type 1-e inclusions in the same samples.
The homogenization of CO2 (Th(CO2)) in this inclusion type Type 2 inclusions: H2O-NaCl inclusions show clear differ-
shows a wide temperature range in all the studied deposits and ences in composition, salinity and homogenization tempera-
within individual fluid inclusion assemblages. The majority tures between early and late generations. The occurrence of
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240
TABLE 3. Summary of the Microthermometric and Raman Spectrometric Data for Fluid Inclusions from Mineralized Veins at Gara
Salinity1 Salinity2
FI VCO2 Tm(CO2) Te Tm(ice) Tm(cl) Th(CO2)(L) Ts Th(L) Th(V) Td (wt % (wt % ρCO2 ρtot CO2* N2* CH4*
type Range (%) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) NaCl) NaCl) (g/cm3) (g/cm3) XH2O XNaCl XCO2 (mol %) (mol %) (mol %)

Type I quartz veins (samples PT5a, PT6, PT8, G10, LD28, LD32, LD41, LD45)
1-e Min –58.2 –53.5 0.513 90.7 0.0 0.0
Max –56.6 31.0 1.168 100.0 9.3 0.0
Mean –56.8 12.9 0.839 98.6 1.4 0.0
0361-0128/98/000/000-00 $6.00
N 171 201 360 20 20 20
1-l Min –57.4 –0.1 0.707

Max –56.6 25.3 0.929
Mean –56.7 15.0 0.822
N 53 53 75
2-l Min –38.8 –20.4 140 13.5 0.995 0.917 0.046

Max –25.9 –9.6 197 22.6 1.066 0.954 0.083
Mean –33.3 –14.7 158 18.4 1.032 0.936 0.064
N 23 21 24 24 21 21 21
3-e Min 10 –58.1 –6.0 –15.8 251 279 200 4.5 0.596 0.676 0.322 0.008 0.028 96.6 0.0 0.0
Max 80 –56.6 7.7 30.0 341 330 325 21.3 1.013 1.010 0.952 0.071 0.577 100.0 3.4 0.0
Mean 35 –56.7 –0.4 15.9 291 313 281 16.0 0.814 0.932 0.753 0.043 0.173 99.4 0.6 0.0
N 113 113 34 121 14 4 16 34.0 121 121 34 34 34 6 6 6
4-e Min 5 –57.6 13.7 283 258 36.9 37.3 0.654 1.235 0.610 0.162 0.017
240
Max 25 –56.6 28.1 372 380 44.5 62.6 0.833 1.481 0.805 0.357 0.104
Mean 10 –56.7 23.0 341 316 41.7 48.8 0.732 1.342 0.710 0.245 0.046
N 22 22 22 10 22 10 22 22 22 22 22 22
LAWRENCE ET AL.
Reactivated type II veins (samples G4, G5, LD27)

1-e Min –75.0 –25.1 0.728 58.3 0.0 0.0
Max –56.6 23.8 0.908 100.0 18.5 32.7
Mean –59.7 4.8 0.741 85.1 5.0 9.9
N 60 61 60 20 20 20
3-e Min 15 –96.0 –4.7 –11.5 269 320 9.6 0.720 0.850 0.322 0.011 0.060 57.0 0.0 2.5
Max 85 –57.1 4.6 19.2 334 328 20.2 0.831 1.034 0.910 0.059 0.667 95.8 15.5 27.6
Mean 60 –60.8 –0.7 4.7 312 324 15.7 0.736 0.917 0.590 0.034 0.377 85.3 3.6 11.1
N 27 27 5 25 3 2 5 25 5 5 5 5 11 11 11
4-e Min 10 –62.8 4.1 250 42.0 0.676 1.269 0.623 0.199 0.032
Max 20 –56.7 14.1 334 57.1 0.745 1.413 0.769 0.322 0.079
Mean 15 –60.5 9.7 303 49.2 0.708 1.343 0.695 0.252 0.050
N 8 8 8 8 8 8 8 8 8 8
Notes: e and l = early and late inclusions, respectively; type 1 = CO2-(N2)-CH4 inclusions; type 2 = H2O-NaCl inclusions; type 3 = H2O-CO2-NaCl inclusions; type 4 = multiphase H2O-CO2-NaCl-
FeCl2 inclusions. Tm(CO2) = melting temperature of CO2 phase; Te = eutectic melting temperature; Tm(ice) = final ice melting temperature; Tm(cl) = clathrate melting temperature; Th(CO2)(L) = homoge-
nization temperature (to the liquid phase) of CO2 phase; Ts = dissolution temperature of halite; Th(L) = final homogenization temperature (to the liquid phase); Th(V) = final homogenization temperature
(to the vapor phase); Td = decrepitation temperature; ρCO2 = density of CO2-rich phase; ρtot = bulk density; XH2O, XNaCl and XCO2 = mole fractions of H2O, NaCl and CO2 (incl. N2 and CH4), respectively;
CO2-N2-CH4* = molar compositions of the gaseous phase determined by Raman analysis; for type 4 inclusions, salinity1 = salinities calculated from Ts and salinity2 = salinities calculated from volumet-
ric proportions of different phases; densities calculated using microthermometric and Raman data

TABLE 4. Summary of the Microthermometric and Raman Spectrometric Data for Fluid Inclusions from Mineralized Veins at Yalea Main
Salinity
FI VCO2 Tm(CO2) Te Tm(ice) Tm(cl) Th(CO2)(L) Ts Th(L) Th(V) Td (wt % ρCO2 ρtot CO2* N2* CH4*
0361-0128/98/000/000-00 $6.00
type Range (%) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) NaCl) (g/cm3) (g/cm3) XH2O XNaCl XCO2 (mol %) (mol %) (mol %)
Yalea Main Central zone (samples PT26, 07YD17, 07YD18, 07YD60, 07YD69, 08YD10)
1-e Min –58.1 0.6 0.707 79.9 4.3 0
Max –56.7 25.3 0.837 95.7 20.1 0
Mean –57.3 14.3 0.743 87.6 12.4 0
N 76 71 71 18 18 18
1-l Min –57.9 9.1 0.654

Max –56.9 28.1 0.781
Mean –57.3 17.6 0.717
N 8 8 8
2-e Min –24.9 –8.9 176 280 0.7 0.606 0.002 0.957
Max –21.0 –0.4 350 300 12.7 0.980 0.043 0.998
Mean –22.0 –4.4 237 290 7.0 0.873 0.022 0.978
N 19 36 32 2 36 32 32 32
241
2-l Min –29.9 –20.7 176 17.8 0.967 0.916 0.059
Max –21.2 –14.0 247 22.8 1.041 0.941 0.084
Mean –23.5 –17.9 202 20.9 1.017 0.926 0.074
N 9 11 11 11 11 11 11
3-e Min 25 –58.1 4.2 12.2 243 247 3.0 0.689 0.803 0.492 0.005 0.086 79.9 7.3 0
Max 75 –57.0 8.5 26.2 297 284 10.2 0.766 0.996 0.891 0.031 0.503 92.7 20.1 0
Mean 35 –57.4 6.7 19.3 270 264 6.1 0.712 0.940 0.795 0.017 0.188 88.9 11.1 0
N 11 11 11 11 3 8 11 11 11 11 11 11 7 7 7
Yalea Main Southern zone (samples 08YD24, 08YD29, 08YD30)

1-e Min –65.7 –5.5 0.620 49.1 4.6 2.6
Max –57.8 29.3 0.789 91.4 45.7 12.3
Mean –59.6 10.6 0.664 76.3 17.8 5.9
N 74 75 78 27 27 27
Notes: e and l = early and late inclusions, respectively; type 1 = CO2-(N2)-CH4 inclusions; type 2 = H2O-NaCl inclusions; type 3 = H2O-CO2-NaCl inclusions; Tm(CO2) = melting temperature of CO2
phase; Te = eutectic melting temperature; Tm(ice) = final ice melting temperature; Tm(cl) = clathrate melting temperature; Th(CO2)(L) = homogenization temperature (to the liquid phase) of CO2 phase; Ts
FLUID INCLUSION AND STABLE ISOTOPE STUDY AT THE LOULO MINING DISTRICT, MALI
= dissolution temperature of halite; Th(L) = final homogenization temperature (to the liquid phase); Th(V) = final homogenization temperature (to the vapor phase); Td = decrepitation temperature; ρCO2
= density of CO2-rich phase; ρtot = bulk density; XH2O, XNaCl and XCO2 = mole fractions of H2O, NaCl and CO2 (including N2 and CH4), respectively; CO2-N2-CH4* = molar compositions of the gaseous
phase determined by Raman analysis; densities calculated using microthermometric and Raman data
241

TABLE 5. Summary of the Microthermometric and Raman Spectrometric Data for Fluid Inclusions from Mineralized Veins at Yalea North, Baboto, and Loulo-3
242
Salinity1 Salinity2
FI VCO2 Tm(CO2) Te Tm(ice) Tm(cl) Th(CO2)(L) Ts Th(L) Th(V) Td (wt % (wt % ρCO2 ρtot CO2* N2* CH4*
type Range (%) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) (ºC) NaCl) NaCl) (g/cm3) (g/cm3) XH2O XNaCl XCO2 (mol %) (mol %) (mol %)

Yalea North (samples PT29, PT30, 07YD11)
1-e Min –58.5 –21.8 0.727 81.4 0.0 0.0
Max –56.6 23.9 1.041 100.0 10.9 10.0
Mean –57.2 6.3 0.888 92.0 5.4 2.5
0361-0128/98/000/000-00 $6.00
N 29 29 29 17 17 17
3-e Min 10 –57.6 –5.8 1.5 272 261 4.1 0.756 0.829 0.338 0.007 0.060 89.2 0.0 0.0
Max 85 –56.6 7.9 21.6 351 295 21.1 0.919 0.978 0.952 0.066 0.667 98.7 9.1 2.0
Mean 40 57.0 2.0 14.1 317 275 13.2 0.830 0.926 0.728 0.035 0.377 92.9 6.0 1.1
N 9 9 9 9 6 3 9 9 9 9 9 9 3 3 3
4-e Min 5 –57.8 13.3 341 281 41.6 37.2 0.702 1.251 0.585 0.162 0.018
Max 20 –56.9 25.6 353 360 42.7 62.4 0.836 1.513 0.803 0.347 0.088
Mean 10 –57.4 19.7 347 317 42.2 50.1 0.774 1.361 0.692 0.258 0.051
N 10 10 10 2 10 2 10 10 10 10 10 10
Baboto (samples BAB2, BAB3, BAB10)

1-e Min –64.9 –14.3 0.671 70.6 0.0 0.0
Max –57.7 12.8 0.843 93.4 14.2 19.4
Mean –62.1 2.0 0.747 82.9 7.2 9.9
N 50 50 50 15 15 15
242
2-e Min –23.8 –7.2 201 253 1.5 0.836 0.964 0.005
Max –22.0 –0.9 291 320 10.7 0.940 0.995 0.036
Mean –22.9 –4.4 240 291 7.0 0.872 0.978 0.022
LAWRENCE ET AL.
N 11 14 11 3 14 11 14 14
Loulo-3 (sample L3-5)

1-e Min –59.3 0.5 0.711 79.7 5.3 0.0
Max –57.2 20.1 0.836 94.7 20.3 1.1
Mean –58.0 10.4 0.769 87.3 12.5 0.2
N 15 15 15 5 5 5
2-e Min –23.7 –6.8 183 5.5 0.888 0.966 0.018

Max –22.3 –3.4 257 10.2 0.959 0.982 0.034
Mean –23.2 –5.6 216 8.6 0.918 0.972 0.028
N 5 6 6 6 6 6 6
3-e Min 20 –58.5 5.8 3.4 252 279 2.0 0.715 0.798 0.241 0.002 0.070 83.1 3.2 0.0
Max 90 –57.4 9.0 24.8 309 284 7.8 0.831 0.982 0.912 0.022 0.757 96.8 16.9 0.0
Mean 45 –58.0 6.9 16.9 272 282 5.8 0.739 0.916 0.702 0.015 0.284 90.0 10.0 0.0
N 7 7 7 7 5 2 7 7 7 7 7 7 2 2 2
Notes: type 1-e = early CO2-(N2)-CH4 inclusions; type 2-e = early H2O-NaCl inclusions; type 3-e = early H2O-CO2-NaCl inclusions; type 4-e = early multiphase H2O-CO2-NaCl-FeCl2 inclusions.
Tm(CO2) = melting temperature of CO2 phase; Te = eutectic melting temperature; Tm(ice) = final ice melting temperature; Tm(cl) = clathrate melting temperature; Th(CO2)(L) = homogenization temperature
(to the liquid phase) of CO2 phase; Ts = dissolution temperature of halite; Th(L) = final homogenization temperature (to the liquid phase); Th(V) = final homogenization temperature (to the vapor phase);
Td = decrepitation temperature; ρCO2 = density of CO2-rich phase; ρtot = bulk density; XH2O, XNaCl and XCO2 = mole fractions of H2O, NaCl and CO2 (incl. N2 and CH4), respectively; CO2-N2-CH4* =
molar compositions of the gaseous phase determined by Raman analysis; for type 4 inclusions, salinity1 = salinities calculated from Ts and salinity2 = salinities calculated from volumetric proportions of
different phases; densities calculated using microthermometric and Raman data

XCO2 = mole fractions of H2O, NaCl and CO2 (including N2 and CH4), respectively; CO2-N2-CH4* = molar compositions of the gaseous phase determined by Raman analysis; densities calculated using
Notes: type 1-e = early CO2-(N2)-CH4 inclusions; type 2-e = early H2O-NaCl inclusions; type 3-e = early H2O-CO2-NaCl inclusions; Tm(CO2) = melting temperature of CO2 phase; Te = eutectic melt-
ing temperature; Tm(ice) = final ice melting temperature; Tm(cl) = clathrate melting temperature; Th(CO2)(L) = homogenization temperature (to the liquid phase) of CO2 phase; Th(L) = final homogenization
temperature (to the liquid phase); Th(V) = final homogenization temperature (to the vapor phase); Td = decrepitation temperature; ρCO2 = density of CO2-rich phase; ρtot = bulk density; XH2O, XNaCl and
type 2-e inclusions in gold-bearing quartz is only seen in the
(mol %) (mol %) (mol %)

CH4*
0
0
0
38
0
0
0
9
Yalea-style veins. This inclusion type exhibits uniform first ice
melting temperatures (or eutectic temperatures; Te), ranging
from –24.9° to –21.0°C (mean of –22.4°C), indicating the
4.0
36.4
18.5
3.1
26.9
13.5
N2*
dominance of Na+ cations (Diamond, 2003). Final ice melting
38
9
temperatures (Tm(ice)) occur between –8.9° and –0.4°C (Fig.
8A), equivalent to salinities of 0.7 to 12.7 wt % NaCl (mean at
CO2*
63.6
96.0
81.5
73.1
96.9
86.5
6.9 wt % NaCl). The homogenization of type 2-e inclusions
38
9
(to the liquid phase; Th(L)) shows a major temperature range
from 176° to 350°C, with the majority clustering between
0.065
0.756
0.172
XCO2
200° and 270°C (mean of 235°C) (Fig. 8B). Five inclusions
36
TABLE 6. Summary of the Microthermometric and Raman Spectrometric Data for Fluid Inclusions from Barren Veins at Loulo
decrepitated (Td) between 253° and 320°C. Bulk densities

range from 0.606 to 0.980 g/cm3.
0.001
0.039
0.022
0.003
0.039
0.016
XNaCl
Type 2-l inclusions, observed at Yalea Main and Gara, are

57
36 far less common than type 2-e inclusions and show notably
lower final ice melting temperatures, between –20.7° and
0.866
0.999
0.976
0.239
0.924
0.811
XH2O
–9.6°C (Fig. 8A). These Tm(ice) values are representative of

57
36
higher salinities of 13.5 to 22.8 wt % NaCl equiv (mean of

19.3 wt % NaCl). Eutectic melting temperatures vary among
(g/cm3)
0.672
0.814
0.701
0.816
0.980
0.910
0.804
1.037
0.972
ρtot
samples. At Yalea Main, Te is similar to type 2-e inclusions

160
54
36
(–29.9° to –21.2°C; mean of –23.5°C), whereas in the first

vein stage at Gara, Te display a bimodal distribution with a
(g/cm3)
0.674
0.905
0.740
ρCO2
dominant cluster from –38.8° to –31.6°C (presence of iron

36
chlorides; Diamond, 2003). Type 2-l inclusions are low-tem-

perature fluids with Th(L) from 140° to 247°C (mean of 172°C)
Salinity
NaCl)
(wt %
0.2
11.7
6.7
1.2
11.7
7.0
(Fig. 8B), and contain higher and more uniform bulk densi-
57
36
ties with ρtot ranging from 0.995 to 1.066 g/cm3. A few type 2-
l inclusions exhibit liquid/vapor metastability. No correlation
(ºC)
250
291
274
16
is observed between salinity and Th for both type 2-e and 2-l
Td
inclusions.
Type 3 inclusions: The majority of the early H2O-CO2-NaCl
Th(V)
(ºC)
197
259
225
4
inclusions display CO2 melting and homogenization tempera-

tures analogous to type 1-e inclusions within the same fluid
inclusion assemblage, and on a wider scale, within the same
Th(L)
(ºC)
167
273
205
54
249
289
261
16
sample or deposit. This is good evidence that type 1-e and 3-

e inclusions are genetically linked. Gara-style deposits show
high Tm(CO2), mainly between –57.0° and –56.6°C (Fig. 9A);
Th(CO2)(L)
–0.4
27.3
15.4
–11.6
27.2
13.8
(ºC)
excluding samples of Gara stage 2 veining, which show Tm(CO2)

160
71
of –96.0° to –57.1°C. Type 3-e inclusions at the Yalea-style de-

posits (Yalea Main and Loulo-3) exhibit Tm(CO2) between
Tm(cl)
(ºC)
3.2
9.4
6.8
–58.5° and –57.0°C (Fig. 9A), implying the presence of addi-

36
tional gases apart from CO2. Partial homogenization (Th(CO2)(L))

of type 3-e inclusions occur over a wide range in all deposits
Tm(ice)
(ºC)
–8.0
–0.1
–4.2
(similar to type 1-e inclusions) between –15.8° and 30.0°C

57
(mainly between 5.0° and 30.0°C) (Fig. 9B).

The salinity of the aqueous phase in type 3-e inclusions
–27.9
–20.8
–23.6
(ºC)
varies between Gara- and Yalea-style mineralized zones. At

Te
38
Gara and Yalea North, melting temperatures of clathrates

(Tm(cl)) show a scattered pattern between –6.0° to 7.9°C (Fig.
Tm(CO2)
–59.3
–56.6
–57.8
–59.8
–56.6
–57.7
(ºC)
9C), indicative of a wide salinity range from 4.5 to 21.3 wt %

microthermometric and Raman data
114
63
NaCl equiv (mean of 15.6 wt % NaCl). Yalea-style orebodies

show distinctly higher and more uniform Tm(cl) of 4.2° to
VCO2
(%)
20
90
30
36
9.0°C (Fig. 9C), corresponding to lower salinities of 2.0 to

10.2 wt % NaCl equiv (mean of 6.0 wt % NaCl). The salini-
ties calculated for type 3-e inclusions at Yalea Main and
Range
Mean
Mean
Mean
Max
Max
Max
Min
Min
Min
Loulo-3 are similar to coexisting type 2-e inclusions.

N
The final homogenization temperatureof type 3-e inclu-

sions is difficult to measure because the majority (~50%) of
inclusions decrepitated prior to homogenization between
type
200° and 328°C (Fig. 9D). Inclusions homogenized into both

1-e
2-e
3-e
FI
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244 LAWRENCE ET AL.
Type 1
250 BV A 200 B
L3
200 160
BAB
150 120
Frequency
Frequency
YM
100 YN 80
GA
50 40
N = 650 N = 723
0 0
-50 -25 -20 -15 -10 -5 0 5 10 15 20 25 30
Tm CO2 (°C) Th CO2 L (°C)

FIG. 7. Tm(CO2) and Th(CO2)(L) histograms for CO2-(N2)-(CH4) inclusions (type 1) at Loulo. Early and late inclusions at Gara
and Yalea Main are not separated as they show similar results (see Tables 3 and 4 for the full microthermometric data break-
down). Tm(CO2) = melting temperature of CO2; Th(CO2)(L) = homogenization (to the liquid phase) temperature of CO2. GA =
Gara, YN = Yalea North, YM = Yalea Main, BAB = Baboto, L3 = Loulo-3, BV = barren veins.
the liquid (Th(L)) and vapor (Th(V)) states (due to the range in Type 4 inclusions: Limited microthermometric data are col-
CO2 modal proportions) between 243° and 309°C at the lected from early H2O-CO2-NaCl-FeCl2 inclusions because
Yalea-style deposits (mean of 273°C), and from 251° to 351°C these inclusions are, in many cases, too small to measure (usu-
at the Gara-style deposits (a higher mean of 300°C) (Fig. 9E, ally <10 μm) and had a tendency to decrepitate prior to com-
F). Type 3-e inclusions show a positive correlation between Th plete or partial homogenization. Type 4-e inclusions, which
and salinity in the Gara-style deposits, whereas Yalea-style are confined to Gara-style veins, show CO2 melting tempera-
orebodies show no clear correlation (Fig. 10A). However, this tures comparable to type 1-e and 3-e inclusions in same in-
inclusion type in the Yalea-style deposits does show a positive clusion assemblage. Gara type I veins and samples from Yalea
correlation between salinity and molar H2O concentrations North show Tm(CO2) ranging from –57.8° to –56.6°C. Type II
(XH2O)) (Fig. 10B). veins at Gara show a scattered Tm(CO2) pattern down to
Type 2
40 BV- e 40
A B
35 L3- e 35
30 BAB- e 30
25 YM- e 25
Frequency
Frequency
20 20
YM- l
15 15
GA- l
10 10
N = 145 N = 138
5 5
0 0
-24 -22 -20 -18 -16 -14 -12 -10 -8 -6 -4 -2 0 150 175 200 225 250 275 300 325 350 375 400
Tm ice (°C) Th L (°C)

FIG. 8. Tm(ice) and Th(L) histograms for early and late H2O-NaCl inclusions (type 2) at Loulo. Tm(ice) = final ice melting tem-
perature, Th(L) = homogenization temperature (to the liquid phase). BAB = Baboto, BV = barren veins, GA = Gara, L3 =
Loulo-3, YM = Yalea Main, e = early inclusions, l = late inclusions.
0361-0128/98/000/000-00 $6.00 244

Type 3
120 A 70 B
BV
60
100 L3
50
80 YM
Frequency
Frequency
40
60 YN
30
40 GA
20
20 N = 230 N = 244
10
0 0
-50 -25 -20 -15 -10 -5 0 5 10 15 20 25 30

50 20
C D
40
15
Frequency
Frequency
30
10
20
N = 102 N = 42
5
10
0 0
-6 -4 -2 0 2 4 6 8 10 12 150 175 200 225 250 275 300 325 350 375 400
Tm cl (°C) Td (°C)
25 5
E F
20 4
Frequency
Frequency
15 3
10 2
N = 44 N = 16
5 1
0 0
150 175 200 225 250 275 300 325 350 375 400 150 175 200 225 250 275 300 325 350 375 400
Th L (°C) Th V (°C)
FIG. 9. Tm(CO2), Th(CO2)(L), Tm(cl), Th(L), Th(V) and Td histograms for early H2O-CO2-NaCl inclusions (type 3-e) at Loulo.
Tm(CO2) = melting temperature of CO2 phase, Th(CO2)(L) = homogenization temperature (to the liquid phase) of the CO2 com-
ponent, Tm(cl) = melting temperature of clathrates, Td = decrepitation temperature, Th(L) = homogenization temperature (to
the liquid phase), Th(V) = homogenization temperature (to the vapor phase). BV = barren veins, GA = Gara, L3 = Loulo-3,
YM = Yalea Main, YN = Yalea North.
–62.8°C (Fig. 11A). Homogenization of CO2 (to the liquid prior to complete dissolution. Only inclusions with a single
phase) cluster between 4.1° and 28°C (Fig. 11B). “visible” grain of halite (≤10 vol %) dissolved, whereas more
Dissolution temperatures of the solid phases (Ts) in type 4-e multiphase solid inclusions (2–4 visible daughter minerals)
inclusions are constrained as 70% of the inclusions decrepitated contain Ts greater than Td (although Fe chlorides were close
0361-0128/98/000/000-00 $6.00 245

246 LAWRENCE ET AL.
25 12
GA A YM B
Salinity (wt.% NaCl equiv) YN 10 L3
Salinity (wt.% NaCl equiv)

20
YM
8
15 L3
BV 6
10
4
5
N = 60 2 N = 18
0 0
150 200 250 300 350 400 0 0.2 0.4 0.6 0.8 1
Th L (°C) X H2O
FIG. 10. Binary plots for H2O-CO2-NaCl (type 3-e) inclusions at Loulo. A) Homogenization (to the liquid phase; Th(L)) vs.
salinity showing a positive correlation for Gara-style orebodies (Gara and Yalea North) and no correlation for Yalea-style ore-
bodies and barren veins. The correlation observed at the Gara-style deposits could be extended to higher Th(L) and salinities
if type 4-e inclusions were included; although, only rough salinities could be estimated from this inclusion type and only min-
imum homogenization temperatures were measured as all inclusions depreciated prior to Th(L) (see Fig. 11). B) Mole frac-
tions of H2O (XH2O) vs. salinity. Only data from Yalea-style deposits are shown to avoid clustering of data (inclusions from
Gara-style deposit show no correlation and barren veins show limited range in XH2O). More aqueous rich inclusions show
higher salinities (salt fractionated in the aqueous phase). BV = barren veins, GA = Gara, L3 = Loulo-3, YM = Yalea Main,
YN = Yalea North.
Type 4
25 16
YN A B
20
GA 12
Frequency
Frequency
15
8
10
N = 40 4 N = 40
5
0 0
-50-25-20-15-10 -5 0 5 10 15 20 25 30

7 14
C 12
D
6
5 10
Frequency
Frequency
4 8
3 6
2 4
1 2
N = 12 N = 40
0 0
150 175 200 225 250 275 300 325 350 375 400 150 175 200 225 250 275 300 325 350 375 400
TS (°C) Td (°C)
FIG. 11. Tm(CO2), Th(CO2)(L), Ts, and Td histograms for early, multiphase, H2O-CO2-NaCl-FeCl2 inclusions (type 4-e) at
Loulo. Tm(CO2) = melting temperature of CO2 phase, Th(CO2)(L) = homogenization temperature (to the liquid phase) of the CO2
component, Ts = dissolution temperature of halite, Td = decrepitation temperature. GA = Gara, YN = Yalea North.
0361-0128/98/000/000-00 $6.00 246

to complete dissolution at Td). Ts measurements of halite A CO2

occur between 283° and 372°C (Fig. 11C), corresponding to 22 and 3 pure CO2
salinities of 36.9 to 44.5 wt % NaCl equiv. These salinities are
only estimates as they do not take into account the presence Gara-style deposits CO2
10
of FeCl2 or any other salt in solution. Approximate estimates GA 90
YN
of salinity (±10%) using the volumetric proportions of differ-
ent phases at room temperature (see Shepherd et al., 1985) Yalea-style deposits CH4 N2
20
YM
indicates a full salinity range from 36.9 to 62.6 wt % total dis- L3
80
solved solids (TDS) (mean of ~45 wt % TDS). None of the BAB
type 4-e inclusions showed complete homogenization prior to 30
decrepitation (Td between 250 and 380°C; Fig. 11D). Type 4- 70
e inclusions contain the highest estimated bulk densities of
the four inclusion types, with a mean of 1.351 g/cm3. 40
60
Barren quartz veins
N = 151
Fluid inclusions in the late (post-ore) barren vein samples
show similar characteristics at Gara and Yalea Main, and con- CH4 40 30 20 10 N2
sist of type 1-e, 2-e, and 3-e inclusion assemblages. Late in-
clusions are not measured microthermometrically (too small; CO2
<2 μm). B
Type 1 inclusions: Early gaseous inclusions show two dis-
tinctive features in comparison to the mineralized quartz 10
veins: (1) there is a distinct lack of high-density (>1 g/cm3) in- GA BV 90
clusions; and (2) Th(CO2) is more homogeneous (± 5°C) within YM BV
individual fluid inclusion assemblages (but vary between dif- 20
ferent assemblages or more commonly different samples). 80
Tm(CO2) occurs between –59.3° and –56.9°C (Fig. 7A) and
Th(CO2)(L) from –0.4° to 30.1°C (mainly 10°–25°C) (Fig. 7B), 30
with estimated bulk densities between 0.672 to 0.814 g/cm3. 70
Type 2 inclusions: Aqueous inclusions show uniform mi-
crothermometric characteristics, with Te ranging from –27.9° 40
to –20.8°C and Tm(ice) from –8.0 to –0.1°C (Fig. 8A). This 60
range in ice melting temperatures corresponds to estimated
salinities between 0.2 to 11.7 wt % NaCl equiv (mean of 6.7 N = 47
wt % NaCl). The homogenization of type 2-e inclusions (Th(L)) CH4 40 30 20 10 N2
occurs between 167° and 273°C (mean of 205°C) (Fig. 8B).
Type 3 inclusions: Mixed aqueous-carbonic inclusions show FIG. 12. CO2-N2-CH4 ternary diagrams showing the gas fluid composi-
Tm(CO2) between –59.8° and –57.0°C (Fig. 9A), Th(CO2)(L) tions (mol %) of early CO2-rich (type 1-e) and early H2O-CO2-NaCl (type 3-
e) inclusions in mineralized (A) and nonmineralized (B) quartz veins at
mainly from –3.4° to 27.2°C (Fig. 9B), and positive Tm(cl) val- Loulo. The two inclusion types show no systematic difference in composition
ues between 3.2° and 9.4°C (Fig. 9C), corresponding to salin- within individual samples, and therefore are not separated here (see Tables
ities of 1.2 to 11.7 wt % NaCl equiv (mean of 5.9 wt.% NaCl). 3–6 for full breakdown). BAB = Baboto, BV = barren veins, GA = Gara, L3
Homogenization temperatures display a narrow range, mainly = Loulo-3, YM = Yalea Main, YN = Yalea North.
to the liquid phase, between 249° and 289°C (Fig. 9E, F).
Approximately 50% of the type 3-e inclusions decrepitated
prior to Th between 250° and 291°C (Fig. 9D). The micro- quartz at the Gara-style deposits are characterized by CO2 ±
thermometric data collected in the barren veins are similar to CH4 compositions (± minor N2). The scatter in the Gara data
results obtained from Yalea Main and Loulo-3 mineralized shown in Figure 12A reflects the differences in gas composi-
veins, but with slightly lower homogenization temperatures. tion between the vein generations. Inclusions in type I veins
are dominated by CO2, with the minority showing low
Raman Spectroscopy amounts of CH4±N2 (≤10 mol %). Type II veins exhibit
The second part of the fluid inclusion study includes a de- greater CH4 concentrations and, in some cases, higher N2 lev-
tailed Raman spectroscopic analysis of 198 selected type 1-e els, with CO2-N2-CH4 ratios of 57.0 to 100 mol %, 0 to 18.5
and 3-e (volatile phase) inclusions. Type 1-l inclusions and the mol % (mainly <5 mol.%), and 0 to 32.7 mol %, respectively.
hypersaline type 4-e inclusions were generally too small for Raman analysis of type 1-e and 3-e inclusions from aurifer-
Raman analysis. The Raman data are plotted in Figure 12 and ous vein quartz at the Yalea-style deposits shows CO2-N2 ±
the ranges (min, max, and mean) are presented in Tables 3 to CH4 compositions. At Yalea Main, there are variations in fluid
6. The gas compositions are similar for both inclusion types in composition along the strike of the deposit. Inclusions mea-
individual samples but vary between the different styles of sured from the central part of the orebody exhibit CO2-N2
Loulo mineralization, and between mineralized and nonmin- compositions between 79.9 and 95.9 mol % and 4.3 and 20.1
eralized veins. Type 1-e and 3-e inclusions from gold-bearing mol %, respectively, whereas type 1 inclusions from samples
0361-0128/98/000/000-00 $6.00 247

248 LAWRENCE ET AL.
collected from the southern zone show CO2-N2-CH4 ratios of 13A) despite clear differences in location and generation.
49.1 to 91.4 mol %, 4.6 to 45.7 mol %, and 2.6 to 12.3 mol %, Mineralized quartz veins from Gara (type I and II veins) and
respectively (Fig. 12A). Raman analysis also detected the Yalea Main show δ18O of 16.1 to 16.8‰ (N = 9; mean of 16.4
presence of graphite-amorphous carbon (broad peak around ± 0.2‰) and 15.8 to 16.3‰ (N = 7; mean of 16.1 ± 0.2‰),
1350 cm–1) in CH4-bearing inclusions from mineralized respectively. These data agree well with two analyses by
samples (Gara-style deposits and particularly the Yalea-style Fouillac et al. (1993) on quartz mineralized veins from Gara
deposits). Late barren quartz veins at Gara (type III veins) (16.1–16.6‰). Late barren veins from both deposits are in-
and Yalea Main are characterized by CO2-N2 compositions distinguishable from the mineralized veins, with δ18Oquartz of
between 63.6 and 86.9 mol % and 36.4 and 3.1 mol %, re- 15.9 to 17.0‰ (N = 4; mean of 16.4 ± 0.4‰). Hydrothermal
spectively, with the notable of absence of CH4. Raman results albite from the proximal (pre-ore) alteration zone at Yalea
are in strong agreement with CO2 melting temperatures Main exhibits slightly lower, but not significantly different,
(Tm(CO2)) from individual samples. δ18O values of 15.6‰ (N = 2).
On the whole, the δ18O data collected from carbonate min-
Stable Isotope Study erals are slightly more variable than the δ18Osilicate data (Fig.
The oxygen, carbon, and sulfur isotope data for Gara and 13B). However, the Gara mineralized veins analyzed in this
Yalea Main are presented in Table 7. The data from this study study again display a remarkably uniform δ18Oankerite values of
are compared to previous work by Fouillac et al. (1993) on 15.1 to 15.6‰ (N = 9; mean of 15.4 ± 0.2‰). The δ18Ocarbonate
the first discovered Loulo deposits (Gara, previously known dataset reported by Fouillac et al. (1993), for mineralized
as Loulo-0, Loulo-3, and P-64) (data summarized in Table 7). zones at Gara, are wider ranging from 15.5 to 19.5‰ (N = 5;
The minor tourmaline-bearing P-64 orebody is located in the mean of 16.9 ± 1.7‰). Only two mineralized veins were ana-
south of the Loulo district (satellite lode of the Gounkoto de- lyzed at Yalea Main due to the lack of carbonate veining at
posit; Fig. 1) and is classified by Lawrence et al. (2013) as a this deposit. Sample 08YD-10 contains an isotopic composi-
Gara-style deposit. tion comparable to the Gara vein carbonates (15.1‰), whereas
sample 07YD-69 shows an anomalous δ18Oankerite value of
Oxygen isotopes 23.2‰. Yalea hydrothermal ankerite from the surrounding
The measured δ18Osilicate values are remarkably homoge- alteration zone (temporally associated with albite) exhibits
neous (within error of reproducibility in each deposit) (Fig. slightly lower δ18O mineral compositions between 13.5 to
16 16
BV A B WR P64
12 YM 12 BV YM
Frequency
Frequency
GA GA
8 8
LS: N = 23
FS: N = 10
4 LS: N = 23 4
FS: N = 3
0 0
13 14 15 16 17 18 19 20 13 15 17 19 21 23 25
δ 18Osilicate V -SMOW (‰) δ 18Ocarbonate V -SMOW (‰)
6 WR BV C 12 D SP P64
5 P64 YM 10 L3 YM
4 8 GA
GA
Frequency
Frequency
3 LS: N = 23 6
FS: N = 10 LS: N = 23
2 FS: N = 30
4
1 2
0 0
-27.5 -22.5 -17.5 -12.5 -7.5 -2.5 2.5 5 7 9 11 13 15 17
δ 13CV-PDB (‰) δ 34SV-CDT (‰)
FIG. 13. δ18Osilicate, δ18Ocarbonate, δ13C and δ34S histograms for mineralized and nonmineralized rocks at Loulo. The dataset
includes isotopes measured in this study (LS) and a previous study of Fouillac et al. (1993) (FS). BV = barren veins, GA =
Gara, L3 = Loulo-3, SP = unaltered syngenetic-diagenetic pyrite, WR = unaltered calcitic and dolomitic wall-rock marbles,
YM = Yalea Main, P64 = P-64.
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TABLE 7. Stable Isotope Dataset for the Loulo Deposits
Silicates Carbonates Sulfides Silicates Carbonates Sulfides
δ18O (‰ vs. δ18O (‰ vs. δ13C (‰ vs. δ34S (‰ vs. δ18O (‰ vs. δ18O (‰ vs. δ13C (‰ δ34S (‰ vs.
V-SMOW) V-SMOW) V-PDB) V-CDT) V-SMOW) V-SMOW) vs. V-PDB) V-CDT)
Sample no. Qtz Cal Dol/Ank Py Sample no. Qtz Alb Cal Dol/Ank Py Aspy
Gara mineralized zones P-64 mineralized zones (cont.)

PT-5 – – 15.2 –10.5 15.2 *C1-44.0 – – – – – 6.9 –
PT-6 16.1 – – – 15.5 *C1-41.5 – – – – – 7.7 –
PT-8 16.6 – – – – *C1-43.9 – – – – – 7.3 –
PT-9 – – 15.4 –11.9 – *C3-35.6 – – – – – 7.8 –
G-7 16.2 – – – – *C14-60.85 – – – – – 6.7 –
LD-13 – – 15.4 –13.7 14.1 *C12-45.3 – – – – – 8.4 –
LD-20 – – 15.6 –11.6 13.6 *C14.58.8 – – – – – 8.0 –
LD-28 16.5 – – – – *C4-75.5 – – – 19.1 –8.5 – –
LD-30 – – – – 13.8 *C4-31.75 – – – – – 9.5 –
LD-31 – – 15.5 –13.1 – *C4-41.95 – – – – – 10.5 –
LD-32 16.4 – 15.5 –9.7 – *C4-34.5 – – – – – 8.7 –
LD-38 – – – – 14.5 *C10-58.0 – – – – – 8.8 –
LD-41 16.8 – – – – *C4-64.5 – – – – – 8.6 –
LD-44 – – 15.6 –14. 4 11.7 *C4-38.2 – – – – – 9.1 –
LD-45 16.2 – 15.1 –11.6 13.3 *C13-68.0 – – – – – 9.5 –
LD-46 – – 15.2 –8.6 11.5 *C6-120.7 – – – – – 9.7 –
G-5 16.1 – – – – *C14-58.8 – – – – – 7.0 –
LD-27 16.5 – – – –
LD-51 – – – – 14.3 Yalea Main mineralized zones
LD-53 – – – – 12.5 PT-18 – – – – – 7.3 6.4
*C13-100.55 16.6 – 16.0 –5.9 12.1 PT-20 – – – – – 8.0 6.6
*C23-26.0 – – – – 12.9 PT-26 15.8 – – – – 8.8 –
*C23-198.3a – – 17.7 –6.5 – 07YD-17 16.3 – – – – 9.6 –
*C23-198.3b 16.1 – 19.5 –4.5 12.5 07YD-18 16.1 – – – – – –
*C23-198.55 – – – – 12.9 07YD-60 16.0 – – – – 8.3 –
*C14-112.5 – – 15.5 –5.1 – 07YD-65 – – – – – 7.1 5.8
*C6-41 – – 15.7 –7.2 – 07YD-69 – – – 23.2 –15.8 – –
*C2-17.75 – – – – 12.9 07YD-71 – – – 14.4 –21.5 – –
07YD-76 – – – 14.2 –21.7 7.7 –
Gara barren veins 07YD-80 – 15.6 – – – – –
LD-11 16.4 – – – – 08YD-10 16.0 – – 15.1 –19.5 – –
G-39 17.0 17.4 – –0.2 – 08YD-24 – – – 13.5 –15.9 – –
G-40 – 21.1 – –1.7 – 08YD-29 16.3 – – – – – –
*C13-114.7 16.4 – 15.1 –2.0 – 08YD-30 16.2 – – – – – –
*C23-84 – – 16.9 3.8 – 08YD-31 – 15.6 – – – – –
08YD-33 – – – 14.8 –16.1 – –
Unaltered Gara calcitic and dolomitic marbles
G-13 – 23.2 – 1.3 – Yalea Main barren veins
LD-16 – 20.7 – –0.4 – 07YD-90 15.9 – 16.4 – –1.7 – –
LD-26 – 23.3 – 0.1 –
*C23-26 – – 22.2 0.5 – Unaltered Yalea dolomitic marble
07YD-52 – – – 20.0 –2.9 9.0 –
P-64 mineralized zones 07YD-53 – – – 19.9 0.4 – –
*C2-52 – – 16.9 –7.0 – 07YD-89 – – – – – 6.4 –
*C3-51.9 – – – – 8.9
*C1-46.0a – – – – 9.2 Loulo-3 mineralized zones
*C1-46.0b – – – – 8.7 *C4-18.20 – – – – – 9.2 –
*C1-46.0c – – – – 8.1 *C4-21.00 – – – – – 7.8 –
*C12-72.4 – – – – 6.0 *C4-16.00 – – – – – 8.9 –
*C2-54.9 – – – – 6.7
Notes: *Fouillac et al. (1993) samples; see Table 1 for descriptions on the Lawrence samples and refer to the Fouillac paper for the others; V-CDT = Vi-
enna Cañon Diablo Troilite, V-PDB = Vienna PeeDee Belemnite, V-SMOW = Vienna Standard Mean Ocean Water; Alb = albite, Ank = ankerite, Asp = ar-
senopyrite, Cal = calcite, Dol = dolomite, Py = pyrite, Qtz = quartz
14.8‰ (N = 4; mean of 14.2 ± 0.6‰). In comparison to the in this present study) are calculated using fractionation equa-
mineralized zones, barren calcite veins from both studies dis- tions of various minerals (quartz: Matsuhisa et al., 1979; al-
play more heterogeneous δ18O mineral compositions be- bite: Zheng, 1993; ankerite and calcite: Zheng, 1999) and es-
tween 15.1 to 21.1‰ (N = 5; mean of 17.4 ± 2.3‰). timated temperatures of mineralization (see Table 8).
The δ18Ofluid compositions derived from the silicate and car- Estimated δ18Ofluid compositions are similar for both quartz
bonate dataset (using only the measured δ18O data collected and ankerite in gold-bearing veins at Gara and Yalea Main,
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250 LAWRENCE ET AL.
TABLE 8. Measured δ18OV-SMOW (‰) and Calculated Values for Coexisting Fluid (data from present study)
Deposit/barren phase Sample type Mineral phase δ18Omineral (‰ vs. V-SMOW) T (°C) δ18Ofluid (‰ vs. V-SMOW)
Gara Vein Qtz 16.1–16.8 340 (min) 10.5–11.2

Ank 15.1–15.6 10.0–10.5
Yalea Main Vein Qtz 15.8–16.3 295–340 8.8–10.7
Ank 15.1–23.2 8.8–18.1
Alt Alb 15.6 11.0–12.1
Ank 13.5–14.8 7.2–9.7
Barren Vein Qtz 15.9–17.0 250–295 7.0–10.1
Cal 16.4–21.1 9.0–15.7
Notes: Temperature estimates based on microthermometric data and chlorite geothermometry (see “P-T conditions”); Alb = albite, Alt = alteration, Ank
= ankerite, Cal = calcite, Qtz = quartz
ranging from 9 to 12‰ (ignoring sample 07YD-69). These pyrites from unaltered Yalea wall rock show similar composi-
values are analogous (albeit more homogenous) to oxygen iso- tions (6.4 to 9.0‰; N = 2) to hydrothermal sulfides in the
tope studies at Ashanti (Mumin et al., 1996; Oberthür et al., mineralized zone. The δ34S range recorded at Yalea Main
1996) and other Precambrian orogenic gold deposits (e.g., closely matches the data collected from Loulo-3 and P-64 by
Kerrich and Fryer, 1979; de Ronde et al., 1992). Fouillac et al. (1993) (6.0–10.5‰; N = 25). The sulfur isotope
composition of the fluid is interpreted to be similar to δ34S
Carbon isotopes compositions of the sulfide minerals because the S-bearing
The carbon isotope dataset for Loulo reveals a wide range fluids appear to have been dominated by H2S (especially at
of carbonate isotope compositions (δ13C) from –21.7 to the Yalea-style deposits) and mineral-H2S fractionation is
+3.8‰ (Fig. 13C). However, there are clear distinctions minimal at temperatures >250°C (Ohmoto and Rye, 1979).
among deposits, mineralized and nonmineralized veins, and
hydrothermal and sedimentary carbonate. First, mineralized Discussion
vein carbonates at Gara show a δ13C range from –14.4 to
–8.6‰ (N = 9; mean of –11.7 ± 1.9‰). Carbon isotopes mea- Interpretation and significance of fluid inclusion
sured in the previous study by Fouillac et al. (1993), from assemblages
mineralized zones at Gara, show slightly higher values of –7.2 The occurrence and distribution of the various fluid inclu-
to –4.5‰ (N = 5; mean of –5.8 ± 1.1‰). The Fouillac et al. sion types at Loulo, though complex, can be best explained by
(1993) study also included the P-64 orebody, with δ13C com- one of four possible mechanisms (or a combination of two or
positions similar to Gara of –8.5 to –7.0‰ (N = 2). In con- more of these): (1) multiple fluid events distinguished by
trast, representative mineralized vein and alteration ankerites chemically and/or physically contrasting fluids trapped at dif-
from Yalea Main exhibit low δ13C signatures of –21.7 to ferent stages, some of which are unrelated to mineralization;
–15.8‰ (N = 6; mean of –18.4 ± 2.8‰). Barren calcite-bear- (2) partial mixing and coeval heterogeneous trapping of two
ing veins from Gara and Yalea Main show notably higher δ13C end-member hydrothermal fluids; (3) phase separation of a
values between –2.0 and 3.8‰ (N = 5; mean of –0.2 ± 2.3‰). homogeneous H2O-CO2-NaCl fluid; or (4) postentrapment
These compositions closely match the δ13C signature of the modifications of a primary or early H2O-CO2-NaCl fluid. The
Kofi calcitic and dolomitic marble wall rocks of –2.9 to 1.3‰ first mechanism can be dismissed for the majority of the ana-
(N = 6; mean of –0.16 ± 1.4‰). lyzed quartz samples because the various fluid types coexist as
early inclusions in the same fluid inclusion assemblages.
Sulfur isotopes However, minor late CO2-rich (type 1-l) and mixed-salinity
The Loulo sulfides show δ34S compositions between 5.8 (13–23 wt % NaCl equiv) H2O-NaCl inclusions (type 2-l) (Th
and 15.5‰ (Fig. 13D). Pyrites from the Gara ankerite-quartz 140°–200°C) are seen in both deposit styles and clearly rep-
vein stockwork show no isotopic differences between the resent postmineralization fluid event(s). The origin of the
mineralized vein generations, with δ34S signatures from 11.5 major inclusion types are examined in the following sections,
to 15.5‰ (N = 11; mean of 13.6 ± 1.3‰). This range is wider with seemingly different mechanisms occurring at the Yalea-
than the sulfide data collected by Fouillac et al. (1993) (N = (fluid immiscibility) and Gara-style deposits (fluid mixing).
5; 12.1–12.9‰). Sulfides from the Yalea Main ore zone dis- Fluid immiscibility: The two major coexisting fluid types
play distinctly lower δ34S values between 5.8 and 9.6‰ (N = present in the Yalea-style deposits are CO2-N2 ± CH4 inclu-
10; mean of 7.5 ± 1.2‰). Despite this tight cluster, there are sions (type 1-e) and H2O-NaCl inclusions (type 2-e). The pet-
clear systematic variations between the different stages of sul- rographic, microthermometric, and laser Raman data collected
fide paragenesis at Yalea Main. In mineralized disseminated from these inclusions imply that they are end-member fluids
zones, pyrite crystals (representative of ore stage 1) exhibit of a low-salinity (≤10 wt % NaCl equiv) mixed H2O-CO2-
δ34S compositions ranging from 7.1 to 8.0‰, whereas ar- NaCl fluid, formed during fluid immiscibility. Their coexis-
senopyrites (associated with ore stage 2) show lower values tence with rare H2O-CO2-NaCl (type 3-e) inclusions at Yalea
between 5.8 and 6.6‰. Auriferous vein pyrites contain the Main and Loulo-3, displaying highly variable XCO2 concentra-
highest δ34S values from 8.3 to 9.6‰. Syngenetic-diagenetic tions (0.070–0.757), can be explained by the heterogeneous
0361-0128/98/000/000-00 $6.00 250

entrapment of the aqueous and carbonic end-member fluids. 1982). Instead, these inclusion types are interpreted to be an
This is a common feature of fluid immiscibility (e.g., Robert end product of partial fluid mixing and heterogeneous trap-
and Kelly, 1987). Fluid immiscibility of H2O-CO2-NaCl pri- ping between the following primary ore fluids: (1) a Yalea-
mary ore fluids has been reported elsewhere in West Africa style, reduced (quartz-faylite-magnetite, QFM, buffered),
(Yao et al., 2001; Coulibaly et al., 2008). The likely causes for lower density (<1.0 g/cm3), low-salinity (<10 wt % NaCl
fluid unmixing at Loulo are considered below (see Yalea fluid equiv) CO2-rich-H2O-NaCl-H2S (± N2-CH4) fluid (true XCO2
model). masked by fluid mixing); and (2) a high temperature (>400°C),
Evidence for fluid unmixing in the Yalea-style ores, using high-density (1.35–1.5 g/cm3), hypersaline (~35–50 wt % TDS),
criteria outlined by Ramboz et al. (1982), are as follows: (1) H2O-rich-CO2-NaCl-FeCl2 fluid (XH2O of 0.7–0.8; XCO2 <0.1).
type 1-e and 2-e inclusions appear to have been coevally The presence of hematite and magnetite (in separate inclu-
trapped in the same fluid inclusion assemblages (Figs. 3C, sions) as daughter phases in type 4-e inclusions (Fig. 6B-D)
4B); the dominance of type 1-e over type 2-e inclusions can be imply the oxidation state of the brines was close to the
explained by the contrasting wetting properties of H2O com- hematite-magnetite (HM) buffer. The strong positive correla-
pared to CO2, with respect to quartz (Watson and Brenan, tion between Th and salinity (Fig. 10A) is compelling evidence
1987; Hollister, 1990); (2) the various inclusion types contain for fluid mixing.
similar salinities, gaseous compositions, and CO2 homoge- The appearance of CO2 (type 1-e) inclusions in the same as-
nization temperature ranges (Figs. 7–9), implying a genetic semblages as type 3-e and 4-e inclusions, along with the simi-
relationship; (3) type 3-e inclusions show higher salinities in lar Tm(CO2) and Th(CO2) ranges, suggests a genetic link between
more H2O-rich inclusions (Fig. 10B), which is consistent with the three inclusion types. The CO2-rich inclusions likely
phase separation, as salt is preferentially fractionated into the formed via retrograde boiling of the vapor components dur-
aqueous phase; (4) final homogenization temperatures for ing mixing between two fluids of contrasting salinity and CO2
type 3-e inclusions are higher than the Th for type 2-e inclu- content; a process known as the “salting out effect” (Anderson
sions (the purer CO2 and H2O end-members were trapped at et al., 1992). This model is supported by the identification of
lower temperatures); and (5) the lack of detectable H2O in solid halite crystals intergrown with quartz, with no evidence
type 1-e inclusions is inconsistent with phase separation from of an inclusion cavity (Fig. 6F), as this process might be ex-
a H2O-CO2-NaCl fluid; however, the small size of these in- pected to produce a salt saturated fluid phase and lead to het-
clusions leads to the possibility of a microscopically unde- erogeneous trapping of precipitated halite crystals. However,
tectable aqueous phase (up to 15 vol %) along the inclusion the possibility of extreme necking down on rare occasions,
rims (Hollister, 1990). leading to isolated halite inclusions, cannot be ignored.
Fluid inclusion assemblages in the late barren veins at Gara Post-entrapment modifications: Water leakage and necking
and Yalea Main also show good evidence for fluid unmixing down of H2O-CO2 salt inclusions (Hollister, 1990; Bakker and
from a low-salinity (mean of 6 wt % NaCl equiv) H2O-CO2- Jansen, 1994) has been used to explain the predominance of
N2 primary fluid (following the criteria discussed above). CO2-bearing inclusions (of variable density) in several quartz
Nonetheless, they differ from fluid inclusions in the Yalea- vein-hosted Birimian gold deposits across West Africa
style ore zones in two fundamental ways. First, type 3-e in- (Schwartz et al., 1992; Klemd et al., 1997; Willie and Klemd,
clusions are more common and homogeneous in composition 2004). At Loulo, however, fluid inclusion assemblages show
(XCO2 mainly between 0.065 and 0.172), and it is therefore little evidence of reequilibration, although the model cannot
suggested that these inclusions are representative of the par- be ruled out completely. To minimize the chances of measur-
ent fluid rather than of heterogeneous mixtures of the two ing reequilibration inclusions, studies were concentrated on
end-member phases. The appearance of the parent fluid in quartz cores which are largely undeformed and measure-
the same assemblages as the two immiscible phases (type 1-e ments were restricted to inclusions showing little morpholog-
and 2-e inclusions) implies that these fluid inclusions were ical evidence for necking down or partial leakage (those with
trapped along or close to the solvus. The absence of the orig- obvious tails). Evidence that leaked inclusions had not been
inal fluid phase in inclusion assemblages from the mineral- significantly incorporated into the data sets comes from the
ized veins suggests inclusions were trapped exclusively below similar CO2 densities for type 1-e and 3-e inclusions within
the solvus. Secondly, no CH4 was detected in the gaseous the same assemblage. This argues against a water leakage
phase of the various inclusion types (Fig. 12B), indicating that model, as some CO2 would invariably have been lost along
the late (post-ore) hydrothermal fluids were more oxidizing in with H2O during this process.
comparison to the Yalea-style gold-bearing fluids.
Fluid mixing: Gara-style deposits contain notably different P-T conditions
fluid inclusion assemblages in comparison to the Yalea-style Yalea-style deposits: Mineral geothermometry of ore and
orebodies and barren veins throughout the district. Three alteration phases at Yalea Main and Loulo-3 indicates hydro-
major temporally related inclusion types exist: (1) CO2 ± CH4 thermal temperature ranges of 294° to 367°C and 271° to
± N2 inclusions (type 1-e); (2) mixed-salinity (5–21 wt % NaCl 377°C, respectively (Lawrence, 2010; Lawrence et al., 2013).
equiv) H2O-CO2-NaCl inclusions (type 3-e), with variable P-T modeling of the microthermometric data from the Yalea-
CO2 contents (XCO2 0.040–0.667); and (3) hypersaline, multi- style deposits is presented in Figure 14. Using the intersecting
phase, H2O-CO2-NaCl-FeCl2 inclusions (type 4-e) (Figs. 3D, isochore method (Roedder and Bodnar, 1980), the minimum
4A). These inclusion types clearly show contrasting fluid com- and maximum isochores of coexisting type 1-e and 2-e inclu-
positions and homogenization temperatures that are not in sions record a large P-T range during entrapment for all stud-
accord with the criteria for fluid immiscibility (Ramboz et al., ied deposits (values irrelevant for geological interpretation).
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252 LAWRENCE ET AL.
4 4
229 /cm 3
= 2 cm 3
2 7 /cm 3
176 cm 3
A Yalea Main B Loulo-3
5 7 cm 3
°C
183 c m 3
14
°C
°C
C
14
/
/
16
g
°C
g
8g
g/
0g
°C
0°
/
94
60
9g
88
.91
Type 1-e
.93
0 .7
0.8
.95
0.8
) =2
) =
)
h(L =
h(L =
x. 0
h(L
n.
an
Type 2-e
h(L =
an
12
x. 0
T
12
h(L
n.
)
)
Depth (km) ρ = 2.7 g/cm3

Mi
h(L
T
Me
3
Ma
)
3
Me
Mi
T
T
T
Ma
Chlorite
T
geothermometry
Pressure (kbar)
10 10
2 8 2 8
Mean = 1.55 kbar

Mean = 1.45 kbar 6 3
6
3
/cm g /cm 3
7g 3 36 /cm
.83 g/c
m
4 0.8 69
g
4
1 .0 43 1 x. 0.7
Ma
x .7 Ma ea
n
ea n0 M 3
/cm
3
M m 271 311
g/c 294 333 1g 2
707 2
.0 .71 chlorite
0. chlorite
M in. Min
Mean = 320 °C Mean = 315 °C
100 200 300 400 500 600 100 200 300 400 500 600
T (°C) T (°C)
4 4
m3
24 m 3
= 2 g/cm 3
C D
C
Baboto Barren veins
C
m3
5°
g/c
/c
14
0°
14
°C
2g
20
g/c
C
10
24 cm 3
0
01
67 °
7
h(L =
.94
0.9
h(L =
0.8
.980
C
)
g/
6°
=1
)
x. 0
T
an
12 12
an
0
T
x. 0
)
Depth (km) ρ = 2.7 g/cm3

h(L
6
Me
3 3
Me
Ma
0.8
h(L)
T
) =
Ma
T
h(L
n.
T
Pressure (kbar)
Mi
10 10
2 8
2 8
Mean = 1.8 kbar
cm
3
6 6
g/ Mean = 1.25 kbar
3
43
29 g/cm
3
.8 m
3
.0
C
g/c cm 3
g/
1°
1 ax 47 4 1 m 4
36
M .7 14 1 g/c
0.8
n0 0 . 8
0.7
0
ea
=
3 x. an
in.
M
/cm Ma Me
)
h(L
3
M
g /cm
T
671 2 2g 2
. 0. .67
Min Min
. 0 Mean = 270°C
Mean = 360 °C
100 200 300 400 500 600 100 200 300 400 500 600
T (°C) T (°C)
FIG. 14. Isochores for minimum, maximum, and mean bulk densities for early CO2-(N2)-(CH4) inclusions (type 1-e) and
early H2O-NaCl inclusions (type 2-e) from Yalea-style mineralized quartz veins and barren veins. A 95% confidence level was
used for Yalea Main bulk density data. Restricted zones of entrapment (shaded areas) are shown using intersections with
chlorite geothermometry (Lawrence, 2010; Lawrence et al., 2013).
The spread in bulk densities could be the result of fault-valve data gives a P-T range of 294° to 333°C at 1.25 to 1.90 kbar
processes (Sibson, 2001; Sibson et al., 1988), whereby fluid and 271° to 311°C at 1.20 to 1.85 kbar for Yalea Main and
pressures fluctuate from near lithostatic to hydrostatic condi- Loulo-3, respectively (Fig. 14A, B). The Baboto target, in the
tions (a common process in active shear zones). In addition, extreme northeast of the Loulo permit, shows slightly higher
calculated density inaccuracies of type 1-e inclusions could be mean P-T trapping conditions of 360°C at 1.8 kbar (Fig.
a contributing factor if these inclusions contain undetectable 14C), corresponding to a mineralization depth of 6.8 km.
H2O along the inclusion walls. A mineralization temperature of 330°C at Yalea Main is also
Nevertheless, P-T values calculated from mean isochores suggested using oxygen isotope fractionation differences be-
are comparable to mineralization temperatures estimated tween paired quartz-ankerite δ18Ofluid compositions (Mat-
from other geothermometric data, implying that they repre- suhisa et al., 1979; Zheng, 1999) for sample 08YD-10 (assum-
sent a good approximation for trapping conditions. Yalea ing coeval precipitation of the two mineral phases). No
Main (Central zone) and Loulo-3 share comparable P-T val- temperatures could be calculated from the oxygen isotope
ues of 320°C at 1.45 kbar and 315°C at 1.55 kbar, respectively data for the pre-ore albite-ankerite alteration samples at Yalea
(Fig. 14A, B). Pressure estimates (assuming lithostatic over- Main because of the large isotopic fractionation between the
burden) are equivalent to depths of 5.6 to 6 km (mesozonal paired minerals (Table 8) (minerals not precipitated in iso-
emplacement). The intersection of chlorite geothermometry topic equilibrium).
0361-0128/98/000/000-00 $6.00 252

Gara-style deposits: Temperature and pressure estimates at The carbon may have been leached into solution by hydroly-
the time of ore deposition in the Gara-style deposits were not sis reactions (e.g., 2C + 2H2O → CO2 + CH4) (Oberthür et
possible to determine using the microthermometric data be- al., 1996), which explains the appearance of CH4 and solid
cause partial mixing and heterogeneous trapping mask the carbon phases in the gas-rich fluid inclusions (in situ equili-
true composition of the two fluid end-members. However, bration). The sulfur in the Yalea-style deposits also appears to
minimum pressures of 1.4 to 2.2 kbars are inferred from de- have been sourced during metamorphism of the host terrane.
crepitation temperatures (cf. Bodnar et al., 1989). The re- A limited number of apparently unaltered syngenetic-diage-
markable uniformity of the δ18Oquartz and δ18Ocarbonate data netic pyrites show δ34S values (6.4–9.0‰) that overlap the
from gold-bearing veins at Gara (Fig. 13A, B) suggests a cor- ore sulfides (5.8–10.5‰) (Fig. 13D). Mineralized sulfides
responding homogeneity of the hydrothermal δ18Ofluid, cou- show δ34S compositions which are similar to those recorded in
pled with a relatively consistent temperature of deposition. other Paleoproterozoic sediment-hosted orogenic gold de-
Paired quartz-ankerite oxygen isotope equilibria for type I posits (Chang et al., 2008; and references therein), but differ
gold-bearing veins (samples LD-32 and LD-45) indicate crys- significantly to the low δ34S values recorded at the Birimian
tallization temperatures between 311° and 329°C (similar to Ashanti gold deposits in Ghana (–12.6 to –4.6‰; Oberthür et
Yalea-style bodies). This implies that the high temperature al., 1996).
(>400°C) brine had little effect on the temperature of miner- The ultimate source of the gold is currently unclear. But
alization, although other parameters such as salinity and ƒO2 given the ore mineral assemblages (dominated by pyrite),
were clearly affected by the mixing process (discussed below, fluid compositions, and trapping temperatures, gold within
in Gara fluid model). Higher temperatures are, however, the Yalea-style hydrothermal system was likely transported as
recorded from mineral geothermometric data at Gara and bisulfide (HS–) complexes, rather than chloride complexes,
Yalea North between 320° and 447°C (Lawrence, 2010; under reducing conditions at about 300° to 350°C in low
Lawrence et al., 2013). to moderate salinity fluids (Stefánsson and Seward, 2004;
Barren veins: The true trapping conditions of the late bar- Williams-Jones et al., 2009). Deposition of gold from such
ren veins are best estimated using bulk densities measured fluids can take place in response to drops in pressure and
from type 3-e inclusions, as these inclusions represent the temperature and/or changes in compositions accompanying
original fluid. Accordingly, final homogenization tempera- cooling and wall-rock interaction (Neall and Phillips, 1987;
tures of this inclusion type provide minimum trapping tem- Phillips and Powell, 1993; Goldfarb et al., 2005). The evi-
perature conditions of the hydrothermal fluid (e.g., Shepherd dence presented here for the Yalea H2O-CO2-N2-NaCl±CH4
et al., 1985). Minimum Th of 249°C and maximum Td of ore solutions is that gold precipitation is primarily controlled
291°C represent the best temperature range approximation by fluid immiscibility. Phase separation tends to fractionate
for the barren fluids (ignoring the few inclusions which ho- the H2S into the vapor phase, decreasing the ligand activity in
mogenized into the vapor state; probably leaked inclusions). the aqueous phase (Williams-Jones et al., 2009). The depleted
Bulk densities for type 3-e inclusions equate to pressures of δ13C values recorded at Yalea Main suggest that fluid unmix-
0.75 to 2.15 kbar. Mean isochore intersections of coexisting ing was likely caused by the expansion of the H2O-CO2-N2-
type 1-e and 2-e inclusions give P-T values of 270°C at 1.25 NaCl solvus during fluid interaction with carbonaceous hori-
kbar (Fig. 14D). zons (cf. Naden and Shepherd, 1989). This wall-rock interaction
control on gold deposition is supported by the fact that non-
Yalea fluid model mineralizing veins contain more enriched δ13C signatures of
The moderate temperature (270°–340°C), low-salinity –2.0 to 3.8‰ (match the host rock carbonates; –2.9 to 1.3‰)
(≤10 wt % NaCl equiv), CO2-rich-H2O-NaCl-N2-±CH4 fluid (Fig. 13C). Fluctuations in pressure and temperature via
responsible for mineralization at the Yalea-style deposits is fault-valve processes, which is interpreted to control the
consistent with fluids released during regional metamor- spread in bulk fluid densities recorded in the microthermo-
phism of orogenic gold terranes (c.f. Powell et al., 1991). A metric data, could be an additional cause for fluid immiscibil-
metamorphic fluid source is supported by the oxygen isotope ity and gold deposition in these deposits.
data, which show typical metamorphic δ18Ofluid compositions
of between 8.8 and 10.7‰ (Ohmoto and Goldhaber, 1997). Gara fluid model
Metamorphic fluids at Loulo were likely released at higher Fluid inclusion data provide good evidence that gold min-
temperatures in deeper parts of the Birimian crust and later eralization in the Gara-style orebodies was linked to fluid
trapped as they cooled and migrated along upper crustal mixing between a Yalea-style metamorphic fluid and a high
shear structures. temperature (>400°C), high-salinity (~35–50 wt % TDS),
Vapor fluid components such as CO2 and minor N2 were metalliferous (Na-Fe-Ca–base metal), H2O-rich-CO2-NaCl-
likely sourced from devolatization reactions during regional FeCl2 fluid. The composition (notably the high Na-Fe-Cl
metamorphism of the host terrane, as well as indirectly by content) of the second fluid type is indicative of a brine that
fluid-rock interactions. Mineralized carbonate veins at Yalea is either magmatic (Hedenquist and Lowenstern, 1994) or
Main show depleted δ13C values between –21.7 and –15.8‰ evaporitic in origin (Yardley and Graham, 2002). An evapor-
(Fig. 13C). This suggests that the ore fluid was buffered dur- itic brine model is most unlikely for Loulo because no evap-
ing interaction with carbonaceous horizons within the wall- orite units have been reported in the Birimian crust of West
rock marbles, given that organic carbon generally contains Africa. In addition, the high temperature of this fluid favors a
δ13C compositions of –25‰ (Hoefs, 1987) and sedimentary proximal magmatic fluid rather than a greenschist facies
carbonate in the Loulo district show δ13C values close to zero. metamorphic fluid. These metal-bearing brines are similar to
0361-0128/98/000/000-00 $6.00 253

254 LAWRENCE ET AL.
those reported in different types of magmatic-related hydro- zone. Unexposed granites in the Kofi Series have also been
thermal ore deposits (Hedenquist and Lowenstern, 1994; Ul- recognized by recent geophysical surveys underneath the
rich et al., 1999; Rombach and Newberry, 2001). Gara and Gounkoto-P64 deposits. The intrusive stocks have a
Isotopic evidence for a magmatic fluid input at the Gara- D2-D3 origin (Ledru et al., 1989; Dabo and Aïfa, 2010), al-
style orebodies is unconvincing; however, reasonable explana- though the absolute timing of granitoid emplacement and
tions are given to support the fluid mixing model. Carbon iso- gold mineralization at Loulo is not well constrained. The dis-
topes from ankerite veins at Gara and P-64 (δ13C of –14.4 to tinctive Fe-Cu-Ni-REE-W ore-related phases associated with
–4.5‰; Fig. 13C) are higher than values measured at Yalea the Gara-style orebodies is similar to the metal signatures re-
Main, and partly overlap the magmatic δ13C field (–8 to –3‰; ported in the Falémé iron skarn deposits (Milési et al., 1989;
Colvine et al., 1988). These data might suggest that carbon Schwartz and Melcher, 2004). Furthermore, the alteration as-
was sourced from both the magmatic and the more reduced semblages observed at these gold lodes show magmatic fea-
metamorphic fluid end-members. The oxygen isotope com- tures (tourmalinization and albitization) and share affinities
position of the Gara mineralizing fluid show remarkably uni- with hydrothermal alteration associated with surrounding in-
form δ18O values between 10.0 and 11.2‰ (similar to Yalea trusive rocks.
Main), which are not typical for magmatic fluids (magmatic The fluid model for the Loulo district is schematically
oxygen signature generally 5–8‰; Ohmoto and Goldhaber, shown in Figure 15. Fluid mixing at the Gara-style orebodies,
1997). Nevertheless, these higher values could reflect contri- between a metamorphic and magmatic derived fluid, is un-
butions from a more δ18O-enriched magmatic source, such as likely to be a single pass system resulting in catastrophic pre-
fluids derived from peraluminous S-type granitoids (Shep- cipitation of gold, but rather repeated pulses of fluid move-
pard, 1986). The sulfide isotopic composition at the Gara- ment (e.g., via seismic pumping). As with the Yalea fluid
style orebodies (δ34S of 6.0–15.5‰) is not consistent with a model, the source of the gold is unclear. But either fluid is ca-
magmatic sulfur source (magmatic δ34S is typically close to pable of transporting significant amounts of gold under the P-
zero; Ohmoto and Rye, 1979). Instead, the sulfur was likely T-X trapping temperatures determined here. At about 400°C,
sourced and transported by the metamorphic fluid. The under oxidizing conditions, several hundred ppb Au or more
higher δ34S compositions at Gara (δ34S of 11.5 to 15.5‰) could be transported in hypersaline brines as chloride com-
compared to the other Loulo deposits (Fig. 13D) is likely plexes (Williams-Jones et al., 2009). Similar levels of gold
source inherited and reflects local variations in the crustal sul- could be transported as bi-sulfide complexes in metamorphic
fur signature within the Kofi Series. fluids with similar P-T-X properties to the Yalea fluids. As the
A magmatic fluid input to the Gara-style hydrothermal sys- magmatic and metamorphic fluids involved in mineralization
tem is also indicated in the companion paper (Lawrence et at Loulo contained different ligands, as well as gold they car-
al., 2013), based on field relations, and the mineralogy and ried different metals in solution. This accounts for different
geochemistry of the orebodies. The majority of the Gara-style mineralogy observed at the Gara-style and Yalea-style deposits
deposits (excluding Yalea North) occur in close proximity (<2 (Lawrence et al., 2013). The high metal content of the brines
km) to the Falémé granitoids and associated iron skarn de- is shown by the identification of Cu+Ni+W±Pb±Zn±Sr±Ba
posits, albeit on opposite sides of the Senegal-Mali shear within the chloride phases (>2,000 ppm). Metal precipitation
MIXING OF FLUIDS 1 & 2 ZONE OF MINERALIZATION

- changes in T, ƒO2 & pH of the brines TRAP
- retrograde boiling of the CO2-rich 1
fluid due to the “salting out effect” TRAP
- Gara-style deposits
2
SOURCE UNMIXING OF FLUID 2
Migration via seismic pumping with - caused by changes in P, T
1 some degree of conductive cooling by & ƒO2, leading to loss of H2S
interaction with country rock, some - occurred at 300-350 °C
loss of CO2, exchange of Na + Fe between 2-3 kbar
ING - Yalea-style deposits
Magmatic fluid OXIDIZ
RE
H2O-CO2-NaCl-FeCl2
DU
Metals (e.g. Cu, Ni, W, Pb, Au + other metals carried

CI
1 Zn + Au) transported
NG
as bi-sulfide complexes
as chloride complexes
~40-55 wt.% NaCl equiv.;

<5 mol.% CO2
Metamorphic fluid
<10 wt.% NaCl equiv.;
High T fluid (>500 °C) released
>5 mol.% CO2-N2
CO2-N2-H2O-NaCl
from a HM-buffered, Fe-rich,
granitic magma QFM-buffered fluid 2 SOURCE
released during regional
metamorphism at ~400-450 °C
2
FIG. 15. Fluid model based on available fluid inclusion and geochemical data for the Loulo hydrothermal system; identi-
fying likely fluid sources, transport mechanisms, and trapping conditions for orogenic gold mineralization along the Senegal-
Mali shear zone.
0361-0128/98/000/000-00 $6.00 254

from the magmatic fluid is linked to decreases in ƒO2 and tem- between 270°–34°C at 1.4 to 1.8 kbar is consistent with the
perature during fluid mixing. In turn, gold deposition from fluid inclusion, isotope, and chlorite thermometric data. This
the H2S-rich metamorphic fluid end-member is related to reduced (QFM-buffered) fluid is likely to have a metamor-
retrograde boiling of the CO2 phase during mixing with the phic source, as confirmed δ18Ofluid compositions of 8.8 to
more saline brines (salting out effect). 10.7‰ at Yalea Main. Similar low-salinity H2O-CO2-NaCl
mineralizing fluid compositions are reported in other Birim-
Implications for orogenic gold mineralization in ian terranes and in orogenic gold districts worldwide.
West Africa and worldwide In contrast, oxidized (HM-buffered), high-temperature
The low-salinity, reduced, CO2-rich-H2O-NaCl±N2±CH4, (>400°C) magmatic fluids appear to be important in the for-
metamorphic fluid associated with gold mineralization at mation of the Fe-rich Gara-style deposits. This fluid is docu-
Loulo is consistent with many orogenic gold fluid studies mented by the presence of metalliferous (Na+Fe+Ca+Cu+
worldwide (e.g., Goldfarb et al., 1988; Powell et al., 1991; Jia Ni+W+Pb+Zn), hypersaline (~35–50 wt % TDS), multi-
et al., 2000; Kerrich et al., 2000) and for West Africa in par- phase, H2O-rich CO2-NaCl-FeCl2 inclusions. Such inclusions
ticular (Klemd et al., 1996; Yao et al., 2001; Coulibaly et al., have not been widely reported, to date, elsewhere in the Bir-
2008). The presence of a second oxidized, hypersaline, H2O- imian crust. Gold mineralization at the Gara-style deposits
rich-CO2-salt primary ore fluid recorded at the Gara-style de- was related to partial fluid mixing between the brines and the
posits, however, is not widely recognized in this style of gold Yalea-style ore fluids. This is seen by the co-existence of H2O-
deposit (Höppner, 1994; Mishra and Panigrahi, 1999). This CO2-NaCl inclusions of variable salinity (5-21 wt.% NaCl
fluid, interpreted as magmatic in origin, points to the poten- equiv) and compositions (XCO2 between 0.040-0.667). Iso-
tial role of multifluid sources in the formation of orogenic topic evidence for a magmatic fluid input at these orebodies
gold deposits. Gold precipitation linked to these physically is not well defined, with signatures likely diluted during fluid
and chemically distinct hydrothermal fluids encourages the mixing with the more dominant regional metamorphic fluid.
development of a diverse group of gold deposits, distin-
guished by variable mineralization styles, ore and alteration Acknowledgments
paragenesis, and metal associations. This is emphasized by The data presented in this paper forms part of a Ph.D. pro-
the Gara- and Yalea-style orebodies at Loulo (Lawrence et al., ject by D. Lawrence, for which financial and scientific sup-
2013). Fluid mixing between metamorphic and magmatic flu- port by Randgold Resources Ltd is gratefully received. Special
ids along major shear zones, in close proximity to crystallizing thanks must go to company senior geologists J. Holliday and
magmas, can increase metal fertility and lead to the formation R. Harbidge for their valuable input. R. Giddens (Kingston
of world-class orogenic gold deposits. University) is acknowledged for his assistance in electron mi-
Mineralogical and geochemical data collected at Loulo sug- croprobe analysis. The authors would also like to thank the
gest that Birimian magmas played an integral part in the gold technical staff at SUERC, East Kilbride, for their help with
mineralization of the West African craton. A recent study on stable isotope analysis and interpretation. Lastly, critical re-
the geology and mineralogy of orogenic gold deposits along views by G. Olivo and C. McFarlane are greatly appreciated.
the Aféma shear zone in the Aboisso region of southeast Côte
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©2013 Society of Economic Geologists, Inc.

Economic Geology, v. 108, pp. 229–257

Introduction deposits (e.g., Oberthür et al., 1994; Allibone et al., 2002a, b;

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Dialé-Daléma Series Falémé Series Kofi Series

Kakadian-Badon batholith- Calc-alkaline, metaluminous Mauritanides Hercynian

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(A) Gara (B) Yalea NNE-trending, 2nd-

100 0 100 m 200 0 200 m

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Fluid inclusion study Stable isotope study

by University of Cape Town user

Non-mineralized/ unaltered rocks

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Cluster of type 1-e

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Type 2-e LH2O

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A Gara B Yalea Main

Type 1-e, type 2-e and

80 B). Iron chlorides are also observed as green, high birefrigent,

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Fe- chloride K mica

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Inclusion type System Occurrence Microthermometric and Raman data

Yalea-style: Tm(CO2): –65.7° to –56.7°C; Th(CO2)(L): –14.3° to 29.3°C; ρtot: 0.671 to

Yalea-style: Tm(CO2): –57.9° to –56.9°C; Th(CO2)(L): 9.1° to 28.1°C; ρtot: 0.654 to

Yalea-style: Te: –29.9° to –21.2°C; Tm(ice): –20.7° to –14.0°C; Th(L): 176° to

Yalea-style: Tm(CO2): –58.5° to –57.0°C; Tm(cl): 4.2° to 9.0°C; Th(CO2)(L): 3.4° to

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by University of Cape Town user

1-l Min –57.4 –0.1 0.707

2-l Min –38.8 –20.4 140 13.5 0.995 0.917 0.046

Reactivated type II veins (samples G4, G5, LD27)

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1-l Min –57.9 9.1 0.654

Yalea Main Southern zone (samples 08YD24, 08YD29, 08YD30)

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by University of Cape Town user

Baboto (samples BAB2, BAB3, BAB10)

Loulo-3 (sample L3-5)

2-e Min –23.7 –6.8 183 5.5 0.888 0.966 0.018

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(mol %) (mol %) (mol %)

dominance of Na+ cations (Diamond, 2003). Final ice melting

200° and 270°C (mean of 235°C) (Fig. 8B). Five inclusions