Journal of African Earth Sciences 39 (2004) 295–300

www.elsevier.com/locate/jafrearsci

Fluid inclusions and quantitative model for gold precipitation

in the Tiouit deposit (Anti-Atlas, Morocco)
a,* b
Fouad Benchekroun , Abderrahim Jettane
a
Département de Géologie, Faculté des Sciences, B.P. 20, Université Chouaib Doukkali, Eljadida, Morocco
b
Département de Géologie, Faculté des Sciences, B.P. 524, Université Mohamed I, Oujda, Morocco

Available online 1 October 2004

Abstract

In the Tiouit gold deposit (Anti-Atlas, Morocco), a paragenetic study has revealed the existence mainly of two generations of
gold, the earliest one was cogenetic with ferro-arseniferous stage I; the second generation (most important) is associated with the
minerals of a cupro-zinciferous sulphide stage II. A microthermometric study of fluid inclusions demonstrates that the main part
of the gold was introduced by an aqueous solution of relatively low salinity (1.7 m Nacl) and deposited at about 400 °C and 500
bars in microfractures crosscutting early sulphides. A calculated quantitative model for the fluid-mineral interaction demonstrates
that a significant amount of gold (3 mg deposited from 1 kg of solution, i.e. 43% of total gold), transported as bisulphide complexes
(HAuðHSÞ02 , AuHS0 and AuðHSÞ
2 ), can be deposited as a result of a decrease in both H2S activity and oxygen fugacity produced by
the alteration of pyrrhotite into pyrite.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Morocco; Tiouit deposit; Quantitative model; Gold precipitation; Sulphidation

1. Introduction pH change, H2S loss, and oxidation), the present study,

based on detailed fluid inclusions microthermometric
The Tiouit gold deposit situated on the northern study, as well as mineralogical and paragenetic studies,
slope of the eastern Saghro (Anti-Atlas, Morocco), is was undertaken with a view to constrain conditions of
localized in the granodiorite massif of the Upper Pre- the gold-bearing mineral assemblage deposition, and
cambrian II (Fig. 1), intrusive in a sedimentary series, notably to elaborate a model for gold precipitation in
deformed and metamorphosed in the greenschists facies, the Tiouit deposit.
during the major Panafrican phase. The Tiouit gold de-
posit was mined by several companies during the periods
1950–1955 and 1960–1964 with the average ore grade
2. Fluid inclusions
being 15–20 ppm Au, 120 ppm Ag and 0.5–5% Cu. Be-
tween 1982 and 1995 the average grade was 7 ppm Au
The succession of mineralization/alteration stages,
and 57 ppm Ag.
established from fluid inclusions and mineralogical data
Taking into account that several mechanisms may
(Al Ansari and Sagon, 1997; Jettane et al., 1999), is sum-
cause gold precipitation in sulphide-rich bodies (cooling,
marized in Table 1 and briefly described hereafter.

*
Stage I: characterized by [L2I] fluid (< 5 wt.% eq. NaCl,
Corresponding author. Tel.: +212 23 34 23 25; fax: +212 23 34 21
87.
Th = 320 °C, Fig. 2) responsible for the deposition of the
E-mail addresses: fbenchekroun@caramail.com, fbenchekroun@ early Fe–As–S (Cu) mineral assemblages: pyrrhotite,
ucd.ac.ma (F. Benchekroun). arsenopyrite and pyrite with inclusions of chalcopyrite

0899-5362/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jafrearsci.2004.07.039
296 F. Benchekroun, A. Jettane / Journal of African Earth Sciences 39 (2004) 295–300
Fig. 1. The Precambrian inliers of the Saghro massif (Anti-Atlas, Morocco), according to the Saghro-Dadès geological map at 1:200,000 scale.
and gold (very low concentrations), and for the associ-
ated silicification which is well displayed in the subplates
mineralized structures. Since the pyrite, that contains at
some places pyrrhotite inclusions, is not limited in a
given moment of the history of the Tiouit hydrothermal
system (Al Ansari, 1997), we consider, among the differ-
ent replacements (arsenopyrite and pyrite by sphalerite
and chalcopyrite), the transformation of pyrrhotite into
pyrite as a ‘‘hinge stage’’ between the two sulphide
stages.
Stage II: marked by the [L2II] fluid, distinguished
through its average composition of 9 wt.% eq. NaCl
(1.7 m NaCl) and by trapping conditions estimated at
400 °C and 500 bars (Fig. 2). This fluid is considered
as responsible for the precipitation of the Cu–Zn–Au
assemblage (stage II, Table 1), and for the most signifi-
cant gold concentrations (10–20 ppm).
A first hydrothermal event, late- to post-Precambrian
II, would be represented by these two ore-forming fluids
[L2I] and [L2II], evolving by dilution-cooling in a med-
ium temperature and pressure regime. The earlier aque-
ous fluids [L1Sp] and [L1Mp] (15–27 wt.% eq. NaCl,
Th = 330 °C, Fig. 2), probably indicating the end (the
last stage) of crystallization of the Precambrian II
granodiorite massif and/or the later magmatic eventsÕ
influence, are also associated with this first thermal
event.
They were followed by a cooler, oxidizing fluid of
moderate salinity (fluid [L1Mt], 15 wt.% eq. NaCl,
Th  200 °C), most probably responsible for a third epi-
sode characterized by the deposition of gold-hematite.
The final stages of the hydrothermal system ob-
served in the Tiouit deposit, are represented, on the
one hand, by the warm brines (fluid [S], 41 wt.% eq.
NaCl, Th = 345 °C) associated with post-Pan-African
events or representing more recent circulations, and
on the other hand, by the last, cooler, low-salinity
aqueous fluid [L1A] (< 10 wt.% eq. NaCl, Th =
200 °C).
3. Gold deposition process
The process of gold precipitation in the Tiouit deposit
is a matter of controversy. One can nevertheless consider
the following:
(1) No significant oxidation of the surrounding rocks
(presence of hematite, magnetite, or other oxides)
has been observed in connection with the auriferous
paragenesis of the stage II. Therefore, this process is
not involved in the deposition of gold.
(2) The process involving unmixing of an immiscible
CO2-rich fluid, cited as the cause of gold precipita-
tion in many mesothermal gold deposits (Robert
and Kelly, 1987), can be ruled out, as the aqueous
inclusions [L2II] are clearly later than the early car-
bonic inclusions.
(3) The localization of the gold mineralization (stage
II) in microfractures crosscutting early sulphides
indicates that gold deposition might be related to
chemical changes in the ore-forming fluid, induced
by reactions between fluid and sulphide minerals
of the host rock. Such a process has been already
advanced by some authors (Groves et al., 1984;
Hannington and Scott, 1989). Accordingly, the
 F. Benchekroun, A. Jettane / Journal of African Earth Sciences 39 (2004) 295–300
Table 1
Paragenetic sequence in the Tiouit gold deposit
þ
From Al Ansari and Sagon, 1997.
Fig. 2. P–T plot of the paleofluid isochores of the Tiouit gold deposit.
envisaged metallogenic model consists of a gold-
bearing aqueous fluid (stage II) circulating in the
sulphide-rich bodies and precipitating gold in these
bodies.
4. Composition of the infiltrating aqueous solution
We assume that the initial fluid was approximately in
equilibrium with quartz (Q)–potassium feldspar (F)–
muscovite (M) assemblages, as hydrothermal solutions
are commonly buffered by this mineral association (Hel-
geson, 1969; Gibert et al., 1993; 1998; among others),
and that gold deposition resulted from reaction between
the fluid and early sulphides (pyrrhotite).
297
Fig. 3. Variations of fO2, aH2S and gold solubility (dashed curves
labelled in ppm) in the initial solution reacting with the pyrrhotite (Po).
(Py: pyrite; Mt: magnetite). A stands for the infiltrating solution and
the arrows indicates the reaction with pyrrhotite.
From the mineralogical and fluid inclusion data, the
P–T conditions of gold precipitation were approxi-
mately 400 °C, 0.5 kbar and the fluid salinity was
1.7 m NaCl. Values of fO2 are chosen slightly above
those defined by the pyrrhotite–pyrite join (point A,
Fig. 3).
The pH corresponding to the QFM assemblage is
nearly neutral. Under such conditions of salinity, fO2
298 F. Benchekroun, A. Jettane / Journal of African Earth Sciences 39 (2004) 295–300

and pH, gold-chloride complexes (AuCl
2 ) are unimpor- The simplified composition of the infiltrating solu-
tant and gold is mainly transported as bisulphide tion, calculated according to the constraints above, is
complexes (Hayashi and Ohmoto, 1991). Several exper- presented the Table 2 (equilibrium constants and equa-
imental studies of gold solubility in aqueous sulphide tions describing the conservation of mass and charge
solutions in the presence of pyrrhotite and pyrite have are given in Table 3 and in Jettane, 2001). The ionic
been performed (Seward, 1973; Wood et al., 1987; Ren- strength, activity coefficients and molalities of the
ders and Seward, 1989; Shenberger and Barnes, 1989; charged species have been calculated according to the
Hayashi and Ohmoto, 1991; Gibert et al., 1993; 1998). HKF model (Helgeson et al., 1981), and the equation
All authors agree that ðAuHSÞ
2 is the dominant gold system solved by the method of Newton–Raphson. Note
0
complex in neutral to slightly alkaline solutions. Seward that the concentration in HAuðHSÞ2 is superior to the
(1973), Renders and Seward (1989) and Gibert et al. other gold-bearing species (Table 2).
(1993, 1998) found that (AuHS)0 was the dominant gold
species in solutions with acid to neutral pH on the other
hand, Seward (1984), Wood et al. (1987) and Hayashi 5. Mechanism of gold precipitation
and Ohmoto (1991) proposed a neutral complex with
an HAuðHSÞ02 stoichiometry. At a given temperature, the gold solubility is mainly
defined by equilibrium (1) and by equilibrium between
0
Table 2 the dominant gold complex HAuðHSÞ2 and minor aque-
Simplified compositions (moles) of the initial aqueous solution

ous species (mainly H2S, HS and H2).
(buffered with QFM, in equilibrium with gold and pyrite, calculated
0
at point A, Fig. 3) and of that equilibrated with pyrrhotite (400 °C, 500 AuðcÞ þ 2H2 S () HAuðHSÞ2 þ H2 ð1Þ
bars)
Apart from a decrease of temperature, that we do not
Infiltrating solution Solution at saturation
in pyrrhotite take into account here because temperature effects in
natural systems are difficult to evaluate (Romberger,
H2 6.91E
03 1.45E
02
H+ 2.46E
05 2.40E
05 1988; Shenberger and Barnes, 1989), the equilibrium
OH
3.82E
06 3.92E
06 (1) indicates that gold deposition at Tiouit can have
HS
7.89E
04 7.87E
04 been in response either to an increase in H2 activity
HSO
4 2.44E
09 1.16E
10 (reduction), or to a decrease in H2S activity. If the infil-
SO2
1.59E
09 7.83E
11
4 trating solution equilibrated with sulphides only by dis-
HC1 3.82E
04 3.72E
04
Cl
6.53E
01 6.50E
01 solving them, an increase in H2S concentration and
NaCl 9.60E
01 9.60E
01 accordingly an increase in gold solubility would be ex-
Na+ 5.64E
01 5.60E
01 pected. In order to precipitate gold it is necessary to
NaOH 4.46E
05 4.58E
05 envisage a process decreasing aH2S and/or fO2. The
KCl 8.56E
02 8.56E
02
transformation of pyrrhotite into pyrite [sulphidation
K+ 8.94E
02 8.94E
02
KOH 1.77E
06 1.82E
06 reaction (2)] fulfills these requirements.
AuCl
2 9.50E
09 5.96E
09 FeS þ H2 S þ 1=2O2 () FeS2 þ H2 O ð2Þ
AuðHSÞ
2 1.48E
05 9.92E
06
HAuðHSÞ02 2.81E
05 1.83E
05
0
AuHS 1.88E
06 1.25E
06
FeCl02 1.97E
07 4.16E
07
6. Numerical modeling
FeCl+ 1.36E
06 2.87E
06
Fe2+ 4.05E
07 8.54E
07
H2S 2.66E
01 2.50E
01 The previously discussed mechanism has been verified
Log fO2
27.60
28.254 by modeling the interaction between the infiltrating
pH 5.27 5.29 solution and pyrrhotite (at T = 400 °C, P = 0.5 kbar,
Au total (ppm) 7.021 3.029
pH = 5.27, fO2 = 10
27.6). For all reactions, equilibrium

Table 3
Equilibrium constants for reactions involving gold-bearing complexes (400 °C, 500 bars)
Reactions Equilibrium constants Sources
HAuðHSÞ02 þ 1=2H2 ðaqÞ () AuðcÞ þ 2H2 SðaqÞ 5.00 (a)
0
AuðHSÞ þ 1=2H2 ðaqÞ () AuðcÞ þ H2 SðaqÞ 6.23 (b)
AuðHSÞ

2 þ 1=2H2 ðaqÞ () AuðcÞ þ H2 SðaqÞ þ HS


2.23 (c)
AuCl

2 þ 1=2H 2 ðaqÞ () AuðcÞ þ 2Cl

þ Hþ
2.80 (d)
(a) Extrapoled from Hayashi and Ohmoto (1991); (b) Gibert et al. (1998); (c) Gibert et al. (1998) recalculated from the data of Shenberger and Barnes
(1989); (d) Zotov and Baranova (1989) (in Gibert et al., 1998).
 F. Benchekroun, A. Jettane / Journal of African Earth Sciences 39 (2004) 295–300
with the buffer assemblage quartz–K feldspar–muscovite
has been assumed. A simplified mass transfer program
written by B. Moine (Toulouse, France) was used to cal-
culate the composition of the solution after equilibration
with pyrrhotite through reaction (2) (Table 2). The main
results are:
(1) The correlated variations of the aH2S and fO2,
according to equilibrium (2), lead to precipitation
of gold from aqueous bisulphide complexes. Three
mg of gold (43% of total gold) can be deposited
from 1 kg of solution (Fig. 3).
(2) At pyrrhotite saturation, the amount of gold precip-
itated from 1 kg of H2O essentially depends on the
initial values of the total sulphur content (RS) and
of fO2. Indeed, with increasing (RS), keeping fO2
constant by decreasing the initial concentration in
total iron (RFe), an increasing amount of pyrrhotite
is transformed into pyrite and therefore a larger
amount of gold is precipitated. An increase in fO2
of the infiltrating solution at constant (RS), imply-
ing a decrease in (RFe), also results in an increased
mass of gold being precipitated, although of less
significance.
7. Conclusion
The numerical model presented above has been car-
ried out using a simplified program whose flexibility of
utilization allows one to work in any system and all
P–T conditions, for which thermodynamic data are
available. Even though these calculations involve
approximations concerning notably equilibrium con-
stants, they do not affect either the main results or the
consistency of the model. It is of note that ore-bearing
fluids are undersaturated with respect to native gold
and they transport only a fraction of aqueous gold con-
centration which is calculated at saturation. The depos-
ited amount of native gold must clearly be smaller in the
considered process. In conclusion, these results demon-
strate that sulphidation reactions can be efficient proc-
esses for precipitating gold transported as bisulphide
complexes, at relatively high temperature. Also, our re-
sults can explain gold enrichments which have been fre-
quently observed as a consequence of increasing sulphur
activity (Groves et al., 1984; Hannington and Scott,
1989).
Acknowledgments
This study was performed using a mass transfer pro-
gram written by B. Moine (Toulouse, France), to whom
we are grateful. Thanks are also due to M.-L. Pascal and
299
the anonymous reviewer for their suggestions and com-
ments that were most helpful in improving the
manuscript.
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