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Geochemical study of the Sakalol Harralol

geothermal field (Republic of Djibouti):
evidences of a low enthalpy aquifer...
Article in Journal of Volcanology and Geothermal Research November 2016
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Journal of Volcanology and Geothermal Research 331 (2017) 2652
Contents lists available at ScienceDirect
Journal of Volcanology and Geothermal Research
journal homepage: www.elsevier.com/locate/jvolgeores
Geochemical study of the Sakalol-Harralol geothermal eld (Republic of

Djibouti): Evidences of a low enthalpy aquifer between Manda-Inakir
and Asal rift settings
Mohamed Osman Awaleh a,, Tiziano Boschetti b, Youssouf Djibril Soubaneh c, Paul Baudron d,e,f,
Ali Dirir Kawalieh a, Omar Assowe Dabar a, Moussa Mahdi Ahmed a, Samaleh Idriss Ahmed a,
Mohamed Ahmed Daoud a, Nima Moussa Egueh a, Jalludin Mohamed a
a
Centre d'Etudes et de Recherches de Djibouti (CERD), Route de laroport, B.P. 486, Djibouti, Djibouti
b
Department of Physics and Earth Sciences Macedonio Melloni, University of Parma, Parco Area delle Scienze 157/a, 43124 Parma, Italy
c
Dpartement de biologie, chimie et gographie, Universit du Qubec Rimouski, 310, Alle des Ursulines, Rimouski, QC G5L 3A1, Canada
d
Dpartement des gnies civil, gologique et des mines, Polytechnique Montral, C.P. 6079. succ. Centre-Ville, Montral, QC H3C 3A7, Canada.
e
UMR G-EAU, BP 5095, 34196 Montpellier Cedex 5, France
f
GEOTOP Research Center, Montral, Canada
a r t i c l e i n f o a b s t r a c t
Article history: Eighty-six sodium bicarbonate to sodium chloride hot springs and four water wells in the Tadjourah Region of
Received 7 September 2016 Djibouti were investigated for major, minor (B, Br, F, Sr, Li) chemistry and isotope composition of water and
Received in revised form 11 November 2016 dissolved components (87Sr/86Sr, 11B/10B, 13C/12C and 14C of DIC, 34S/32S and 18O/16O of sulfate). The deep saline
Accepted 11 November 2016
Na-Cl reservoir at 143 C shows afnity with the shallow geothermal water from the active Asal rift. Asal water
Available online 14 November 2016
is a diluted and recycled seawater component with the major cation composition obliterated by equilibration
Keywords:
with Stratoid basalt. Locally, the deep reservoir is differentiated in term of recharge, and re-equilibration with
Afar rocks and mixing. In particular, two spring groups reveal contributions from evaporites typical of the passive
Djibouti graben setting of the Afar. A model on 34S/32S and 18O/16O demonstrates the isotope imprint of magmatic SO2 dis-
Hydrogeochemistry proportionation on dissolved and solid sulfate, whose values probably persists in a sedimentary environment
Isotopes without trace of seawater. On the other hand a seawater signature, modied by mixing and secondary fraction-
Geothermometry ation effects, is partially maintained according to the boron isotope composition (up to +27.4). Temperature
Sakalol estimation in low-enthalpy geothermal reservoirs is notoriously difcult, especially where mixing with uids
of differing genesis and/or conduction cooling take place. From a geothermometric point of view, the multi-
method approach followed in this study (up-to-date theoretical and thermodynamic equations, ad-hoc silica
geothermometers inferred from local rocks, checking of the results on a 18Osulfate-water vs. temperature diagram)
provides some insights and perspectives on how to tackle the problem.
2016 Elsevier B.V. All rights reserved.
1. Introduction the Republic of Djibouti for estimating their geothermal potential

(Sanjuan et al., 1990; D'Amore et al., 1998; Awaleh et al., 2015a,b).
As in other rifting zones, the activity of the East African Rift System In the Sakalol and Harralol horst-and-graben structure extending to-
corresponds to large seismic, tectonic and volcanic activities (Barberi wards south down to north the Asal Rift, there are a dozen thermal
et al., 1975; Mlynarski and Zlotnicki, 2001). Such a particular springs. The Sakalol-Harralol geothermal eld (~ 200 km2) is one of
geodynamical situation gives to the Republic of Djibouti a remarkable the largest geothermal elds of the Republic of Djibouti, which is located
position for the development of geothermal energy. Indeed, the in the north of the East Africa Rift. However, due to remote and poorly
Republic of Djibouti features numerous hot springs, fumaroles and accessible sites, the geochemistry of 6 thermal springs from the
hydrothermal alteration mainly distributed in the western part of the Sakalol-Harralol geothermal eld (SHGF) only was reported in the
country and along the Gulf of Tadjourah ridge (Fig. 1A). However, few early seventies (BRGM, 1970). Systematic geochemical sampling and
studies have been completed on areas with geothermal activities in analysis of the numerous hydrothermal springs in SHGF was needed
for a better understanding of the regional geothermal regime of this
Corresponding author. wide area located between two active spreading segments of Asal and
E-mail address: awaleh@gmail.com (M.O. Awaleh). Manda-Inakir (Fig. 1).
http://dx.doi.org/10.1016/j.jvolgeores.2016.11.008
0377-0273/ 2016 Elsevier B.V. All rights reserved.
M.O. Awaleh et al. / Journal of Volcanology and Geothermal Research 331 (2017) 2652 27
The main purpose of the present study is to characterize the hydro- no perennial surface, received an inlet from Lake Asal and fed by direct
thermal activity of the SHGF. Detailed geochemical investigations have precipitation surface runoff from the escarpments walls, and nally by
been carried out for the rst time on the cold groundwaters (well and groundwater.
boreholes waters) and almost all thermal waters (86 thermal springs) The restricted spatial distribution of active hydrothermal manifesta-
from the Sakalol-Harralol area. Environmental and radiogenic isotopes tions only along the hanging wall of the normal faults shows that existing
(2H-H2O, 18O-H2O, 18O-SO2 34 2
4 , S-SO4 , B,
11 87
Sr/86Sr, 13C, 14C) fault structures provide key pathways for the upow of the geothermal
as well as major and minor ions chemistry are applied to assess the geouids (Kerrich, 1986; Norton and Knapp, 1977) (Fig. 1B). Hot springs oc-
chemical evolution and groundwater residence times of the thermal currence seems occupying a specic area along fault zones. To the north,
waters from the SHGF. The results of this investigation are compared the hydrothermal manifestations are located on the high angle steeply
with previous published data on the hot waters from neighboring gra- dipping fault, bounding the northern margin of the sakalol intrabasin.
ben and rift systems. Hot springs are clustered in the central part of the fault where displace-
Boron isotopes (11B) have over the last two decades frequently ment is maximal according to the classical fault growth models predic-
been used to elucidate groundwater salinization and pollution problems tion (Cowie and Scholz, 1992). To the south, the hot springs are
(e.g. Vengosh et al., 1994, 1998, 1999). To the best of our knowledge, in situated at the terminations (fault-tips) of the individual segmented
no study 11B value neither for groundwater nor for thermal waters in faults, limiting both Harralol intrabasin margins (Fig. 1B). Fault overlaps
the East Africa Rift system has been reported. In the present study the zone separating the two Harralol-Haral intrabasin appears to be a favor-
rst results of boron isotopes in thermal waters from the East Africa able site for the development of hot springs (Fig. 1B). Fault-tips and faults
Rift system are reported. overlaps are sites of elevated stress causing active fracturing and contin-
The goals of this study are: (1) to classify the thermal water compo- ual re-opening of uid-ow conduits, permitting long-lived hydrother-
sition data into genetic groups, (2) to characterize the main geochemi- mal ow (Hutchison et al., 2015; Kaya, 2015).
cal processes that explain the thermal waters geochemistry and to The general morphostructural framework of the studied geothermal
understand their geochemical evolution, (3) to estimate the tempera- zone comprises three adjacent structural units with similar morpholog-
ture in the SHGF geothermal reservoir through chemical and isotopic ical features. It consists of a succession of three elongated half-graben
geothermometry and (4) to estimate the eventual scaling processes of structures facing NE and their corresponding intra-basins which are
the SHGF geothermal waters. The results obtained allow for the under- from, south to the north, Harralol, Haral and Sakalol (Figs. 1B and 2).
standing of the behavior of this system on a regional scale and are useful Individual intra-basins are generally less than 3-km-wide, and they
for planning future management of the Sakalol-Harralol geothermal are bounded by N140E striking normal faults, dipping to NE and or-
system. thogonal with respect to the inferred N40E regional tectonic extension
(Gaulier and Huchon, 1991).
2. Geological and tectonic setting The dominant N140E fault set is composed of linear, highly seg-
mented structures showing at their extremity curved and overlapping
The SHGF is located within the northwestern portion of the map traces, N 15 km in length (Figs. 1B and 2). Thus, the fault network
Ghoubbet-Asal, which forms an accretionary emerged rift segment pene- along the Alol geothermal eld displays steeply dipping attitudes and
trating the Afar depression (Varet, 1975). Similar geological features are shows southerly tilted stratoid basaltic blocs (Fig. 2). Very few antithetic
the Manda Inakir, the Manda Hararo and the Erta Ale. The Afar depression fault structures exist, for example, that intersects the northern margin of
is a triple junction characterized by thinned continental crust, where Sakalol intra-basin, facing SW and causing the vertical downthrow of
three rift systems meet: the Red Sea, the Gulf of Aden and the East the Stratoid Basalts towards the sub-rift axis (Fig. 2). It should be
African Rift (Gaulier and Huchon, 1991; Manighetti et al., 1998) (Fig. 1A). noted that these faults and corresponding tilted blocks were developed
The most complete Afar synrift volcanic succession is well exposed on the Makarassou westerly facing monocline exure that lowers the
in the Republic of Djibouti. The oldest units are located in the Ali- Stratoid surface down to the Asal rift oor (Tapponnier et al., 1990; Le
Sabieh region. They consists of a mac intrusion (2028 Ma, Le Gall Gall et al., 2011). The highly elevated (~1650 m) and segmented relief,
et al., 2010) core mantled by an outward-dipping envelope, including occurring further south in the prolongation of the Asal fault system
a Jurassic-Cretaceous sedimentary cover overlain by (i) initial mac ef- corresponds to the footwall of the Doubi master fault (Fig. 2). It pre-
fusive sequences, and (ii) younger acidic series of the 1511 Ma old sents an overall convex-shaped morphology resulting from an active
Mablas Fm (Zumbo et al., 1995). These latter are onlapped by the youn- tectonic uplift (Doubre et al., 2007) (Fig. 2). This fault exhuming a
ger Dalha (8.63.8 Ma) and Somali (7.23.0 Ma) basalts (Chessex et al., large part of the older Dalha series shows a low-angle dip. These ob-
1975) whose oor depressed the area and the Djibouti plain respective- served geometrical features characterize the Doubi fault as a detach-
ly (Fig. 1A). The youngest volcanic units, related to the recent down- ment fault.
faulting and rifting process comprise Stratoid trap-like basaltic series It is commonly observed that systems containing several sub-
b3 Ma, covering most parts of the Afar depression (Varet, 1975; parallel faults that dip and tilt the same way are kinematically coupled
Zumbo et al., 1995), the Tadjourah Gulf Basalts (2.81.0 Ma) associated with basal shear zone (Jackson et al., 1988). Following the wide-scale
with the initiation of Tadjourah rifted zone (Manighetti et al., 1998; conjugate passive margins concept applied to the entire SE Afar exten-
Daoud et al., 2011) and Asal-Ghoubbet and Manda Inakir volcanic at sional domain, Geoffroy et al. (2014) interpreted recent/active pattern
around 900 ka (Manighetti et al., 1998; Audin et al., 2001) are assumed rift kinematics in the Asal/Alol rifted zone in terms of a crustal extension
to represent the axial part rift system (Vellutini, 1990) (Fig. 1A). in which the Doubi fault acted as detachment that merges into the up-
The stratigraphy of the Sakalol-Harralol area comprises the exten- domed part of the basal shear plane, beneath the Asal. Consequently, the
sive Plio-Pleistocene (2.31.0 Ma) Stratoid basalts (Gasse et al., 1987) Makarassou monocline exure is considered a post-magmatic roll-over
which rest unconformably over highly weathered basalts of the Dalha structure developed in the hanging of the Doubi detachment fault
series (Fig. 1B). In addition, the sedimentary inll consists of alluvial, (Fig. 2).
salty silt and hydrothermal deposits (Fig. 1B). The hydrothermal calcite
edices, several meters high, are located in the vicinity of still active 3. Material and methods
thermal springs, in veneer crowning basaltic escarpment. Their con-
struction began during the Asal high stand (ca 6800 yr. B.P) and stable 3.1. Sampling and analytical methods
isotope contents in hydrothermal concretions indicate higher evapora-
tion rates than a previous phase, when a connection existed between A total of eighty six thermal springs, two well waters and two bore-
Asal and Alol (Gasse and Fontes, 1989). The ancient lake had probably hole waters were sampled in April 2015. Temperature ( 0.1 C), pH
28 M.O. Awaleh et al. / Journal of Volcanology and Geothermal Research 331 (2017) 2652
Fig. 1. (A): A schematic geological map of the Republic of Djibouti (SE Afar Rift) and hydrothermal activity of the Republic of Djibouti. (B): A schematic geological map of the Sakalol-
Harralol geothermal eld (C1: Cluster 1 thermal waters; C2: Cluster 2 thermal waters; C3: Cluster 3 thermal waters; C4: Cluster 4 thermal waters; B: Borehole water; WW: Well waters).
In the inset: schematic map of the Afar Depression with the location of Djibouti (black rectangle).
Makarassou
monoc
line
flex
ure
ASAL 1670 m Co
-150 m
nv
ex
Doubi
-shap
f
ul
a
t
e
d mor
Doub
Tilted b
ph o l o
i fau
Ha
Ha
rra
lt
gy
ral
ol
detachment
Sa
locs
alo k
l
~ 4km
Fig. 2. 3D Landsat view of the Doubi detachment fault and tilted blocks developed in the lower part of the Makarassou exure.
(0.01 unit) and electrical conductivity (1 S/cm), were measured deviation from the V-PDB standard, and the error for 13C is 0.05
on site using the following portable instruments: 1) temperature - (mean error obtained from replicate analyses).
CheckTemp(Hanna); 2) pH - pH 610 (EutechInstruments); and 3) con- The 14C activities were measured by accelerator mass spectrome-
ductivity - COND 610 (Eutech Instruments). The instruments were cal- try (HVE 3 MV Tandetron accelerator) at the A.E. Lalonde Laboratory
ibrated in the eld. at the University of Ottawa (Canada). CO2 for 14C analysis was ex-
Water samples were collected into polyethylene containers after l- tracted from water samples in a vacuum and converted to graphite
tration through 0.45 m membrane lters. All samples used for determi- by reducing it with excess hydrogen gas in the presence of a
nation of cations were acidied after collection through addition of preconditioned (reduced) Fe powder catalyst. The 14C results were
Suprapure HNO3 (Merck) to bring the pH below 2. reported as percent Modern Carbon (pMC) with an average 1
Analysis of anions and major cations was carried out with a Dionex error of 0.3 pMC.
ICS 3000 Ion Chromatograph using analytical and quality assurance pro- Water samples for 87Sr/86Sr analyses were ltered through 0.45 m
cedures for geothermal water chemistry, following Pang and membrane lters and acidied to pH b 2 with Suprapure HNO3
Armannsson (2006). (Merck) before being collected into 250 ml polyethylene containers.
Analysis of trace elements (B, Sr) was conducted using an Ultima 2 Sr-isotopes were determined in a VG sector 54 in dynamic mode at
(Horiba Jobin Yvon) Inductively Couple Plasma Atomic Emission Spec- the GEOTOP laboratory (Canada). 87Sr/86Sr ratios were normalized to
87
trometer (ICP-AES). National Institute of Standards and Technology Sr/88Sr = 0.1194. Repeated analyses of the NIST-987 standard yielded
traceable commercial standards were used for quality control. These values of 0.710294 ( 0.000022, 2 reproducibility). Furthermore,
standards were analyzed to within 3% of the known values for trace these results were corrected to the accepted value for NIST-987 of
elements. For the analysis of aqueous SiO2, the water samples were di- 0.710248.
luted tenfold using deionized water to prevent SiO2 polymerization. Samples for sulfur and oxygen isotope analyses were collected at the
SiO2 concentrations were determined by colorimetry and analyzed outlet of columns using 250 ml pre-acid-washed plastic perplex bottles.
using a Jenway 6300 spectrophotometer, while HCO3 was analyzed for Cd-acetate was already added to the bottles (5% v/v) prior to sample
by titration with 0.1 M HCl following Gran method. The charge balance collection (to x sulfur as CdS) and then the aliquot was ltered through
between anions and cations (([Anions] - [Cations])/([Anions] + a 0.2 m nitrocellulose lter before the chemical determination of resid-
[Cations])), concentrations in meql 1, was assessed and analyses ual sulfate. Then, dissolved sulfate was precipitated as BaSO4 at pH b 4
were accepted for deviations of less than 3%. (in order to remove HCO3 and CO2 3 species) by adding a BaCl2 solu-
Additional samples of untreated waters were collected into 50 ml tion. The isotope analysis of BaSO4 was carried out using an IsoChrom
glass bottles (Quorpak) for analysis for stable isotopes of the water mol- Continuous Flow Stable Isotope Ratio Mass Spectrometer coupled to a
ecule (2H-H2O and 18O-H2O). Water samples ltered through 0.45 m Carlo Erba Elemental Analyzer at the Environmental Isotope Laboratory
membrane lters were collected into 1000 ml Nalgene bottles for at the University of Waterloo. Sulfate-isotope ratios are reported in the
carbon-14, and into 250 ml plastic bottles for carbon-13 determinations usual -scale in with reference to V-CDT (Vienna Canyon Diablo Troi-
of dissolved inorganic carbon (13C-DIC). The isotope ratios of hydrogen lite) and V-SMOW (Vienna Standard Mean Ocean Water). Sulfate-
and oxygen were analyzed for at the GEOTOP laboratory at the isotope ratios (34S(SO4) and 18O(SO4)) were determined with a preci-
Universit du Qubec Montreal (Canada) using a Micromass Isoprime sion of 0.3 vs. V-CDT for 34S(SO4) and 0.5 vs. V-SMOW for
isotope ratio mass spectrometer and converted into per mil delta values 18O(SO4).
() versus the Vienna Standard Mean Ocean Water (V-SMOW) stan- Water samples for boron isotope analyses were collected into 500 ml
dard following () = [(Rsample/Rstandard) - 1] 103, where R is the iso- polyethylene containers after ltration through 0.45 m membrane l-
topic ratio of interest (2H/1H or 18O/16O). The average precision, based ters. The B isotope composition was analyzed using a TIMS VG 336 at the
on multiple analyses of various samples and laboratory standards was Tetra Tech Laboratory (USA). The 11B data were reported in per mil
0.1 for 18O-H2O and 0.8 for 2H-H2O. The 13C ratios were de- () relative to the standard of NIST SRM 951. The average value for
termined using a mass spectrometer (Micromass, Isoprime model the NIST SRM 951 standards analyzed with each batch of samples is nor-
with triple universal collectors) at the GEOTOP laboratory (Canada). malized to the accepted isotopic ratio; this correction is applied to the
13
C contents are reported using the conventional () notation as a measurement for each sample in a given batch analyzed in the mass
spectrometer. Subsequently, the standard deviation is computed and member within the group is more similar to its fellow members than
reported as the long-term precision of the isotopic measurement to 1. to any member outside the group (Gler et al., 2002).
In this study, 13 variables (EC, Ca, Mg, Na, K, HCO3, Cl, SO4, NO3, F, Br,
3.2. Data elaboration B, and SiO2) in 90 water samples were analyzed using Q-mode HCA and
PCA.
The computer program R (2016) was used to conduct statistical The result of the HCA is presented as a dendrogram (Fig. S1, see
analysis (Hierarchical Cluster Analysis and Principal Components Anal- supporting information). The HCA allowed us to distinguish four clus-
ysis HCA and PCA). The HCA was performed using a combination of ters (C1C4) of thermal water in the SakalolHarralol geothermal eld
Ward's linkage method (Ward, 1963), adopting the Euclidean distance (Fig. S1): Cluster 1 (less mineralized thermal waters with EC =
as measure of dissimilarity. The PCA was implemented using the 15004740 S/cm); Cluster 2 (thermal waters with EC =
FactoMineR (Factor analysis and data Mining with R) package 42159516 S/cm); Cluster 3 (thermal waters with EC =
(Husson et al., 2009). Calculation of mineral saturation indices, 780412412 S/cm), and Cluster 4 (thermal water with EC =
logP(CO2) and activity of dissolved component were performed using 22660 S/cm). The robustness of the HCA results was veried by relat-
PHREEQCI, version 3 and thermo.com.v8.dat thermodynamic dataset ing the statistically dened clusters to their geographical locations. In
(Parkhurst and Appelo, 2013). This latter and Thermoddem (release fact, the four clusters had shown a well-distinguished distribution,
2014; Blanc et al., 2012) datasets were used to draw mineral stability with good correspondence between spatial locations and the statistical
elds in activity diagrams by The Geochemist's Workbench, version 7 groups (Fig. 1B). Samples that belong to the same group are located in
(Bethke and Yeakel, 2008). Finally, full chemical composition and car- close proximity to one another, suggesting different steps of the
bon isotope data were elaborated together by PHREEQCI and the iso.dat evolutive processes along different ow paths (Gler and Thyne,
dataset to obtain 13C(CO2) from 13C(DIC), whereas Netpath XL was 2004). In other terms, it was reported that waters which fall into a sta-
used to calculate and correct groundwater age using 14C data tistical group may have similar residence times, a similar recharge histo-
(Parkhurst and Charlton, 2008). ry, and identical ow paths or reservoirs (Swanson et al., 2001; Gler
and Thyne, 2004).
4. Results and discussion PCA of water chemical variables from the SHGF produced two com-
ponents (Table S1, see supporting information), accounting for 74.18%
Field data (temperature, pH, electrical conductivity, total dissolved of the total variance of the dataset. The principal component loadings,
solids, sampling locations) major and minor elements and hydrochemical as well as their respective explained variances are presented in
types of all water samples are listed in the supporting information le and Table S1. Loadings, that represent the importance of the variables for
summarized in Table 1. Isotope results are in Table 2. the components are in bold for values greater than 0.7 (Table S1).
Most of the variance is contained in the PC1 (63.12%) which is asso-
4.1. Statistical analysis ciated with the variables EC, Ca, Na, K, HCO3, Cl, SO4, Br and B, with
squared regression coefcients of 0.93, 0.69, 0.98, 0.87, 0.77, 0.98,
HCA and PCA have commonly been used as a quantitative and inde- 0.86, 0.95 and 0.81 respectively. Therefore, PC1 can be used to account
pendent approach for groundwater classication (Meng and Maynard, for a SakalolHarralol thermal waters salinization processes. PC2
2001; Swanson et al., 2001; Gler et al., 2002). HCA is generally used (11.06%) is mainly related to F and SiO2 with squared regression coef-
to classify observations or variables, in order to dene more or less ho- cients of 0.84 and 0.70 respectively. Therefore PC2 is conceived to repre-
mogeneous groups and emphasize their genetic relations (Davis, 1986). sent mainly a dimension that describes mineralization of thermal
In other words, HCA produces the most distinctive groups where each waters from the SHGF by silicate dissolution.
Table 1
Mean chemical and physicochemical parameters of the four statistically determined water groups in the Sakalol-Harralol geothermal eld. See the supporting information le for specic
values in the hot spring and local non-thermal groundwater samples.
Parameter Unit Cluster 1 Cluster 2 Cluster 3 *Cluster 4
NaClHCO3-SO4 NaCl NaCl NaCl
N = 34 N = 31 N = 20 N=1
Mean St.dev. Mean St.dev. Mean St.dev. Mean St.dev.
EC (S/cm) 1928 654 6607 1509 9778 1294 22660 -

pH at sampling temperature 8.22 0.38 8.12 0.32 7.91 0.33 7.16 0.01
T (C) 45.9 4.9 42.2 7.6 45.8 5.9 77.7 1.6
TDS (mg/l) 1043 365 3537 745 5289 596 13265 -
Ca (mg/l) 10.8 5.8 45.0 37.2 112 42 1020 72
Mg (mg/l) 2.82 2.28 6.37 2.11 13.7 8.6 12.9 3.4
Na (mg/l) 380 132 1258 249 1844 285 3653 152
K (mg/l) 14.7 3.4 40.5 12.0 50.1 15.2 119 5.7
Li (mg/l) 0.058 0.060 0.096 0.102 0.119 0.110 1.03 0.12
NH4 (mg/l) 1.05 2.40 0.369 0.395 1.98 5.15 0.53 0.40
HCO3 (mg/l) 197 53 120 42 68 23 3.16 1.38
Cl (mg/l) 366 193 1766 405 2676 409 7073 396
SO4 (mg/l) 164 36 273 52 493 91 399 18
NO3 (mg/l) 15.1 4.3 9.15 4.85 8.10 7.13 2.92 0.40
NO2 (mg/l) 0.040 0.039 0.24 0.40 0.071 0.052 0.030 0.014
F (mg/l) 4.95 0.86 2.62 1.51 4.72 1.08 2.06 0.20
Br (mg/l) 1.21 0.57 5.37 1.56 8.71 1.41 27.1 2.1
SiO2 (mg/l) 92.7 10.2 95.8 9.2 107 11 123 1
Sr (mg/l) 0.062 0.017 0.28 0.14 0.64 0.31 15.9 -
B (mg/l) 0.792 0.172 1.44 0.42 2.67 0.92 3.12 0.02
N: number of sampled springs (2015).

: Cluster 4 is composed of only one spring (Galiceela). Data in these columns refer to two samplings carried out twice (2015 and 2016).
Table 2
Isotope data for the Sakalol-Harralol geothermal eld.
Cluster # Sample Sample name 18O(H2O) 2H(H2O) 13C(DIC) *13C(CO2) 14

C 11B 34S(SO4) 18O(SO4) 87
Sr/87Sr
# ( vs ( vs ( vs ( vs (pmc) ( vs ( vs ( vs
V-SMOW) V-SMOW) V-PDB) V-PDB) SRM951) V-CDT) SMOW)
1 1 douffalou 1 3.90 28.1 - - - 12.8 8.16 11.49 0.7057

4 douffalou 4 3.87 27.6 - - - - 7.60 11.75 0.70530
6 douffalou 6 - - 6.89 13.35 18.10 - - - -
9 ciddayta 3 4.07 28.6 6.08 12.69 19.04 - 8.75 11.87 0.7053
10 halmal 1 3.88 26.4 - - - - 9.67 12.42 0.7061
12 dir dara 1 3.89 28.0 - - - - 8.73 11.43 0.7056
16 konadara 2 3.88 27.4 - - - - 9.88 11.86 0.7055
19 konadara 5 - - 6.54 12.97 20.69 - - - -
21 konadara 7 - - - - - 18.5 - - -
23 konadara 9 - - 6.68 13.42 21.37 - - - -
25 konadara 11 4.04 26.8 - - - - 8.54 11.82 0.7057
30 konadara 16 3.79 25.3 - - - - 9.82 11.92 0.7056
31 As dara 1 3.60 24.6 - - - - 8.63 11.08 0.7054
32 As dara 2 - - 6.74 13.28 20.73 - - - -
33 kouroubta 1 3.22 20.7 - - - - 10.69 11.25 0.7053
well. bore. 35 Dora borehole 0.27 1.20 - - - - 6.60 8.79 0.7063
36 Balho borehole 2.74 18.0 12.97 18.86 29.27 20.5 - - 0.7041
37 hagande well 2 - - - - - 13.5 - - -
2 39 hamadaba 1 3.27 24.4 - - - - 11.46 11.68 0.706
43 hamadaba 8 - - 5.13 12.26 33.07 - - - -
46 hamadaba 11 - - 5.50 12.63 35.63 - - - -
47 hamadaba 12 3.28 21.5 - - - - - - -
49 Dor Asi 1 2.18 15.3 - - - - 12.29 10.38 0.7055
51 Dor Asi 3 1.88 12.9 - - - - - - -
53 ina citta 3 3.49 24.2 - - - - - - -
60 hamadaba 6 3.1 20.3 - - - - 12.54 12.01 0.7058
48 hamadaba 14 - - - - - 24.2 - - -
61 hagand 3 2.22 17.7 7.27 14.30 32.29 - 13.2 11.55 0.7055
62 hagand 6 2.12 14.2 - - - - 12.71 11.24 0.7055
65 As bodara 3 2.94 22.6 - - - - - - -
66 As bodara 1 3.00 23.5 6.95 12.60 21.21 - 9.74 9.96 0.7044
67 As bodara 2 2.87 21.0 - - - 11.4 - - -
3 70 badacii 1 2.25 20.2 - - - - 14.13 11.42 -
71 badacii 2 - - - - - 19.1 - - -
72 badacii 3 2.29 18.5 - - - - 13.66 11.00 0.7044
74 Ina citta 1 - - 6.97 13.11 20.79 - - - -
75 ina citta 2 3.12 23.6 - - - - 8.79 10.16 0.7046
76 hamadaba 4 2.34 19.0 - - - - 13.44 11.25 0.7058
77 birtibodeh 2.29 16.6 - - - - 13.10 11.6 0.7057
78 loubag dara 1.96 17.3 - - - - - - -
79 ali celah - - 4.57 10.74 23.54 - - - -
80 Aden Dara 2.19 19.3 - - - 18.7 - - -
81 houmad nouh 1 2.12 18.0 - - - 21.0 - - -
82 houmad nouh 2 2.15 19.9 - - - - - - -
84 houmad nouh 4 2.26 19.2 - - - - 14.61 11.88 -
86 houmad nouh 6 - - 2.38 8.86 24.47 - - - -
88 houmad nouh 8 - - 3.12 9.81 23.31 - - - -
4 90 galiceela 1.72 12.9 9.75 14.42 25.71 27.4 14.28 11.39 0.7037
: Calculated by PHREEQCI and iso.data thermodynamic-isotopic dataset (Parkhurst and Appelo, 2013).
The water sample observations of the two principal component Hydrogeologists, 1979). Total equivalents of cations and anions
axes are plotted in Fig. S2 (supporting informations). In score plot were separately accepted as 100% and ions with more than 20%
PC1 vs. PC2 (Fig. S2), the water samples could be subdivided into (meq/l) were taken into consideration in this classication. More-
four distinct clusters, which are quite similar to the groupings ob- over, chemical composition of the waters was plotted in anion and
tained by HCA. cation ternary diagrams on weight basis (Fig. 3), the former with
the typical waters elds detected in geothermal areas as described
by Giggenbach (1991a), and Langelier-Ludwig in equivalent basis
4.2. Main hydrochemical features and classication (e.g. Boschetti, 2011; Fig. 4). According to statistical analysis, the
chemical composition of the waters described in terms of relative
Hydrothermal activity in the SHGF is characterized by thermal springs concentrations of the main anions and cations allows the discrimina-
that discharge from faults generally aligned NW-SE (Fig. 1B). The tem- tion of the following four groups of waters (Table 1, Fig. 3):
peratures of the thermal water samples at the SHGF ranged from 38 to
77.7 C, with an average of 45.1 C (Table 1). Geothermal waters are mod- (1) Cluster 1 (C1): less mineralized thermal waters from the SHGF
erately alkaline with an average pH of 8.11 (pH = 7.028.95). (TDS = 7152455 mg.l1) are mostly of the NaClHCO3SO4
Classication of the waters samples in Table 1 was made accord- type. The high alkalinity of these waters is typical of the Rift
ing to the principles of IAH (IAH, International Association of groundwaters where high rate of carbon dioxide outgassing
Obock
ma
tu r
eC
lw
Abhe
a te
rs
T.A.D.D.
Minkileh
s
ter
wa
nic
pe
rip
lc a
Cl
he
vo
ral
/sh
SO4 HCO3
all
ow
wa
te
rs
(dug well)
#35
steam-heated waters
Mg
this study
well-borehole
Ca Na+K
Cluster 1
Sakalol Cluster 2
Cluster 3
Cluster 4
Obock
literature
Abhe T.A.D.D. geothermal well

Oued-Kalou Asal hot spring
Lake Asal
geothermal well
Mg
Hanl borehole
springs
Ca Na+K
seawater
Obock
Abhe T.A.D.D.
Fig. 3. Anions (A) and cations (B1 and B2) ternary diagrams (data in mg/l). Diamonds are hot spring waters and borehole waters from Sakalol (this study). In (A), peripheral/shallow,
volcanic and mature elds are from Giggenbach (1988, 1991a). In both, gray elds depict other geothermal waters from Afar and Djbouti: Obock (Awaleh et al., 2015a); Abhe (Awaleh
et al., 2015b, Houssein et al., 2013; JICA, 2014); T.A.D.D. (Tendaho-Allallobeda-Dobi-Dubti graben system, Ali, 2005; UNDP, United National Development Program, 1973; Panichi,
1995; D'Amore et al., 1997). Water samples from Asal (Bosch et al., 1977; Correia et al., 1985; D'Amore et al., 1998; Sanjuan et al., 1990; JICA, 2014) and Hanl (Aquater, 1986; BFGUR,
1999; Houssein, 2010; JICA, 2014) are also shown for comparison. From this latter area, Minkileh spring and Hanl 1, Hanl 2 geothermal wells have been analyzed in this study
(squares with thick border).
from mantle and which enhances rock water interaction at shal- (4) Cluster 4 (C4): saline thermal water (TDS = 13265 mg.l1) are
low depth (e.g. Kebede, 2013): of the NaCl type. It is represented by the highest temperature
sample from Galiceela (#90).
CO2 H2 O Na; KsilicatesHCO3 Na; K Hsilicates
Notwithstanding the main Na-Cl composition, waters from the SHGF
(2) Cluster 2 (C2): moderately mineralized thermal water (TDS = are rich in sulfate that is typical of geothermal waters in rift settings in
21994790 mg.l1) are of the NaCl type. the region (D'Amore et al., 1997; D'Amore et al., 1998; BFGUR, 1999;
(3) Cluster 3 (C3): brackish thermal water (TDS = 4334 Awaleh et al., 2015b). The concentration increases proportionately
6946 mg.l1) are of the NaCl type. with salinity, therefore distinct sulfate concentrations are revealed
(SO4 + Cl)
T.A.D.D.
50
#35 Na-HCO3 waters 45

sensu stricto
#75
Obock
waters interacting with 40
#90 Abhe sedimentary formations
35
30
(Ca + Mg)
(Na + K)
25
20
A
0 0
0 5 10 15 20 25 30 35 40 45 50
(HCO3)
(SO4 + Cl)
Minkileh
50
Na-HCO3 waters
sensu stricto 45
Dobi
Obock
waters interacting with 40
sedimentary formations
Abhe 35
30
(Ca + Mg)
(Na + K)
25
20
15
10
B
0 0
0 5 10 15 20 25 30 35 40 45 50
(HCO3)
well/borehole
Cluster 1 geothermal well geothermal well
Sakalol Cluster 2 Asal hot spring Hanl borehole seawater
Cluster 3 Lake Asal hot-warm-cold springs
Cluster 4
Fig. 4. Langelier-Ludwig diagram (data in meq/l). Sample symbols as in Fig. 1. In (A), waters from Sakalol (this study) and Asal are plotted. In (B), waters from Hanl. In both, a bricked eld
was depicted by waters interacting with a sedimentary formation in the Hanl eld (Aquater, 1986; Houssein, 2010).
between water groups: C1 = 164 36 mg/l, C2 = 273 52 mg/l, C3 = the literature, the relatively high quantity of sulfate in the East Africa
486 93 mg/l, except Galiceela spring (C4) whose sulfate concentra- Rift System has been linked to the circulation of relatively deep waters
tion was not signicantly different from C3 group: 399 18 mg/l. In within a thick sedimentary surface sequence (D'Amore et al., 1997;
Awaleh et al., 2015b). However, the anions ternary diagram (Fig. 3) 1999; Bosch et al., 1977; Correia et al., 1985; DAmore et al., 1998; Dar-
shows that most of the C1 water group evolves from the HCO3, shallow ling and Talbot, 1991; Fontes et al., 1979, 1980; Fouillac et al., 1989;
(ground)water corner, towards the volcanic waters side at a constant Houssein, 2010; JICA, 2014; Panichi, 1995; Schoell and Faber, 1976;
SO4/Cl ratio of 0.36 0.07. It is interesting to note that this value is sim- Verhagen et al., 1991) and other data from geothermal systems of the
ilar to that revealed in the waters from Hanl-Gaggade (Hanl 1 and 2 Main Ethiopian Rift (M.E.R.) and Ethiopian Afar (Ali, 2005; Craig et al.,
geothermal well: 0.27 0.02, N = 2, BFGUR, 1999; Minkileh spring: 1977; D'Amore et al., 1997; Gonantini et al., 1973; IAEA, 2007; Panichi,
0.37 0.02, N = 3, JICA, 2014, this work) and Dobi (0.24 0.12, 1995). The typical and most evident geothermal 18O-shift was detected
N = 19; UNDP, United National Development Program, 1973, Panichi, in the Danakil depression, in particular in Dallol hot springs waters
1995; Ali, 2005, 2011) grabens, which have a widely sedimentary (Gonantini et al., 1973), but a mixing trend towards basaltic water
cover (e.g. Tesfaye et al., 2008). has recently been suggested after analysis of fumarolic condensates in
Therefore, the origin of sulfate could be related both to a sulfate of the area (Franzson et al., 2015; Taran and Zelenski, 2015). In the case
deep hydrothermal source, as occurring in Asal area (D'Amore et al., of Djbouti hot springs, meteoric and geothermal waters plot very close
1998; Fouillac et al., 1989), and to sulfates of sedimentary origin. to the LMWL (Awaleh et al., 2015a,b). The SHGF samples from this
In the anions ternary diagram, C2 waters plot close to the geother- study conrm this tendency, being mainly grouped near to the LMWL
mal waters of the Ethiopian Afar (T.A.D.D. waters in Fig. 3: Tendaho, at 2H b 10. This deuterium divide is in accord with a deep re-
Allallobeda, Dobi, Dubti) and show a vertical trend up to C4 water, charge for Abhe and Hanl geothermal waters (Awaleh et al., 2015b).
whereas C3 waters resemble the geothermal waters of Lac Abhe. De- Exception is represented by the Dora borehole water (sample # 35)
spite the increase of chloride concentrations in the water groups, clus- which is more shifted towards enriched 2H values similarly to the
ters 1 to 3 fall out of the mature Cl eld similarly to other Afar Rift Wadi-recharged aquifer (Awaleh et al., 2015b), the Awash river and di-
geothermal waters. C4 waters represent the exception, plotting very luted springs from Hanl (e.g. Aquater, 1986). Interpretation of this
close to Asal hot springs samples. The presence of seawater near to sample may be ambiguous because the sample falls within the standard
the chloride apex of the diagram can lead to misleading interpretations deviation of geothermal water from Asal geothermal wells (Fig. 5).
of a direct involvement of this end-member in the SHGF circulation However, its 2H N10 and an alignment on a straight line parallel
(Fig. 3). In fact, it should be noted that a cation diagram shows distinctly to meteoric water lines along with the Balho borehole (#36) and Cluster
that Asal springs plot between seawater and local mature geothermal 1 samples suggests a shallow meteoric recharge, compatible with non-
water, according to their mixed marine origins (D'Amore et al., 1998; evaporated monsoon rains which have generated heavy oods
Fouillac et al., 1989; Sanjuan et al., 1990), whereas most of the SHGF wa- (Awaleh et al., 2015b). Another evidence from the water isotope plot
ters group in the 90% sector of alkali vertex, plot like other Afar hot wa- is that Cluster 1 and Cluster 2 waters from this study show a distribution
ters of mainly meteoric origin (T.A.D.D. eld). In the same cations comparable with the Hallol-Harallol springs water data published
diagram, C4 waters approach Asal geothermal waters plotting like previously (Fig. 5; Fontes et al., 1980, where Hallol-Harallol = Sakalol-
those of Abhe hot springs, but this latter similarity does not appear in Harralol), with Cluster 1 thermal waters showing the most depleted
the anions plot. This means that the cations acquisitions processes are 2H and 18O values in comparison with any other hot spring waters
by water-rock interaction with conditions similar to the Lake Abhe geo- from the study area (Fig. 5, Table 2). In particular, the distribution of
thermal waters, whereas the anion concentrations are controlled by the Cluster 1 samples is between Hanl, Danab and Abhe geothermal wa-
deep gases, mainly SO2/H2S and CO2, and high the amount of chloride ters. The depleted isotope composition of Cluster 1 thermal waters
from the Asal geothermal system. could probably be due to a recharge from meteoric water from a higher
Finally, the Langelier-Ludwig plots combine the informations from altitude than the other SHGF thermal water groups. This recharged
both ternary diagrams (Fig. 4). Here it is evident that all waters from groundwater is probably from Moussa Ali Mountain (altitude
the Sakalol-Harralol are mainly of alkali-chloride type, except that ~ 2021 m) groundwater which ow towards Sakalol-Harralol depres-
from the Dora borehole (#35) which has a Na-bicarbonate signature. sions (BGR, 1982).
The straight line departing from the Na-bicarbonate corner separates Dor Asi and Hagande waters of the Cluster 2 hot springs (#4951
clusters 13 from C4, where the formers are more similar to T.A.D.D. and #6162, respectively) and Balho borehole (#36) groundwater
geothermal waters, whereas the latter to Asal-Abhe geothermal waters (depth ~300 m, T ~62 C) show similar stable isotopes values as Abhe
(Fig. 4a). hot springs, as well as Hanl 2 geothermal water (Fig. 5; Awaleh et al.,
Most of the waters from Hanl show a distribution similar to that of 2015b), whereas Hanl cold boreholes waters were mainly recharged
C1C3 from Sakalol, but with more scattering probably due to a contri- from the regional aquifer (Aquater, 1986; BFGUR, 1999). Therefore,
bution from sedimentary cover. In particular, waters from geothermal these thermal waters from the SHGF should originated from a geother-
wells and boreholes (Hanl 1-2 and R1-R4, respectively; BFGUR, mal reservoir fed by meteoric water mainly from the regional aquifer, as
1999) drilled and sampled in the 1980-1990s plots near that of the is the case with the Lake Abhe geothermal eld (Awaleh et al., 2015b).
Dobi hot springs, whereas Hanl geothermal well waters sampled in All but one Cluster 3 hot springs plot very close to the LMWL, with
2009 (Houssein, 2010) and 2016 (this study) show an increasing contri- values slightly shifted to the right side interpretable as an 18O-
bution of dissolved sulfate or meteoric/sedimentary waters of bicarbon- enriched composition due to water-rock interaction at high tempera-
ate composition, respectively. ture and/or low water/rock ratio (Fig. 5). However, mixing with basaltic
water could not be excluded, considering the similarity between the
4.3. Water isotope composition mixing path depicted with that showed by literature data for Abhe hot
springs (Awaleh et al., 2015b; Fontes et al., 1980).
The oxygen 18O(H2O) and hydrogen 2H(H2O) ratios are useful Finally, the C4, Galiceela (#90) hot spring water in the study area has
tracers for determining the origin of groundwater and are widely used a very similar stable isotopes composition to the Korili hot spring of me-
in studying natural water circulation and groundwater movement. teoric origin from the Asal geothermal eld (JICA, 2014; Fontes et al.,
The stable isotope compositions of the SHGF waters are shown in 1989), located in the south of the study area (Fig. 5). This indicates
Table 2. In Fig. 5, all the data are plotted along with: the Global Meteoric that probably the same meteoric groundwater supplies the geothermal
Water Line (GMWL) 2H(H2O) = 8 18O(H2O) + 10 dened by Craig reservoirs from which Galiceela (#90, C4 thermal water) and Korili/
(1961); the Local Meteoric Water Line (LMWL) as dened by Fontes Oued Kalou hot springs rise up from the SHGF and Asal geothermal
et al. (1980), with the same slope of the GWML but null deuterium ex- elds, respectively. In other terms, this meteoric groundwater transits
cess (d = 0) (Fig. 5, Awaleh et al., 2015a,b); other water isotope data of from the Asal local rift to the Sakalol-Harralol depression without any
Djibouti from literature (Aquater, 1986; Awaleh et al., 2015a,b; BFGUR, signicant change in the isotope content. It has been reported that
this study
well-borehole
20 r n
A Ri
ve
ra
po )
tio Cluster 1
a sh a Cluster 2 Sakalol
Aw seawater ev = 5
10 (S Cluster 3
Lake
Asal Cluster 4
#35
0 literature
M.E.R. Asal
Schoell & Faber 1976
Dallol Fontes et al. 1979, 1980
-10 (hot springs) Adam 1984
H(H2O) ( vs V-SMOW)
Verhagen et al. 1991
-20 mean s.d.

GMWL
(d=10) Dallol Afar and M.E.R.
T.A.D.D.
(fum.cond.) geotermal uids
-30 samples
pooling
Erta Ale geothermal well

-40 Asal
Asal? (fum.cond.) hot spring
2
LMWL
-50 (d=0)
-60
-70
Basaltic
Water
-80
-6 -4 -2 0 2 4 6 8 10
18
O(H2O) ( vs V-SMOW)
-10
B
-12
-14 #90
literature
-16
spring
#36
-18
borehole
-20 Hanl
H(H2O) ( vs V-SMOW)
-22 deep geothermal well

(Hanl 2; BFGUR 1999)
-24
-26
Abhe
Danab
-28
-30
2
-32
-34 Abhe springs

(Fontes et al. 1980)
-36
-38
-40
Asal springs?
-42
-5 -4 -3 -2 -1 0 1
18
O(H2O) ( vs V-SMOW)
Fig. 5. Hydrogen vs. oxygen stable isotope composition. Global (GMWL, Craig, 1961) and local (LMWL, Fontes et al., 1980) meteoric water lines are shown. Sample symbols as Fig. 3, but
open diamonds: SHGF from literature. See the main text for a complete list of the references relating to the samples showed. In (A) and (B), arrows depict hypothetical mixings with
basaltic water (Allard, 1983; Kyser and O'Neil, 1984; Giggenbach, 1991b). In (A), dashed line represents best t of the Awash River data (Ayenew et al., 2008; Panichi, 1995; JICA,
2015; Yitbarek et al., 2012). The line with a slope of about 5, i.e. representing evaporation effect, been traced on the CK sample (Canal Sakalol, Fontes et al., 1980) and extended up to
LMWL. In (B), a detail of Sakalol hot springs waters is shown.
seawater supplies most of the hot springs located northward from the 1989; Sanjuan et al., 1990). Therefore, since there is no isotopic evi-
Lake Asal, while meteoric groundwater supplies Korili and Oued Kalou dence of seawater intrusion from the Asal local rift to the Sakalol-
hot springs located southwestward from Lake Asal (e.g. Fontes et al., Harralol basin, it is more likely that there is an underground connection
only between the South of the Asal local rift and the Sakalol-Harralol de- It is of interest to note that the Galiceela (#90) hot spring in the
pression. The supposed communication of Lake Asal with the northern study area is about 50 km far from Korili hot spring (Lake Asal area).
depressions of Sakalol and Harralol by paleochannels (Gasse and Water from geothermal well Asal 1, drilled in the Lake Asal geothermal
Fontes, 1989) is therefore conrmed by our isotope data. eld, has different stable isotopes ratios and chloride concentration than
Cl (mg/l)
10
H(H 2O) ( vs V-SMOW)
5 seawater
0
A1 well
-5
Korili
-10
-15
-20 5
18
-25 #35
0
-30
-5
Minkileh Oued-Kalou
this study
well-borehole -10
#90
Cluster 1
Cluster 2 Sakalol
-15
Cluster 3 T.A.D.D.
Cluster 4
literature -20
Schoell & Faber 1976 Agna

Verhagen et al. 1991 Abhe
-25
Danab
geothermal well
Asal
hot spring -30
0 1000 2000 3000 4000 5000 6000 7000
spring
Hanl borehole
geothermal well
(Hanl 2; BFGUR 1999)
Dobi waters with Cl > 1 g/l
Cl (mg/l)
2
O(H2O) ( vs V-SMOW)
1 seawater
0 A1 well
-1 Korili
-2
-3 0.5
-4 T.A.D.D.
18
0.0
-5 #35
-0.5
-1.0
Oued-Kalou
-1.5 Minkileh #90
-2.0
-2.5
Abhe
-3.0
Agna
-3.5
Danab
-4.0
-4.5
0 1000 2000 3000 4000 5000 6000 7000
Fig. 6. Water isotope vs. chloride concentration. Symbols as in Fig. 5. Continuous line: high chloride concentration low isotope values limit of the samples from Sakalol. Dashed line:
ttings between A1 well (Fouillac et al., 1989) and sample C4 from this study (#90, Galiceela). Dotted and dashed-dotted lines represent hypothetical ttings of the hot springs from
Hanl and Sakalol with hot springs interacting with alluvial/evaporitic deposits (Oued-Kalou, Bosch et al., 1977; Dobi, Ali, 2005), respectively. T.A.D.D.: Tendaho-Allallobeda-Dobi-
Dubti graben system. See main text for details and complete references list of the samples from literature.
Galiceela (#90) hot spring (Fouillac et al., 1989), but a chloride versus for the application of solute geothermometers (Fig. 7). This diagram
water isotope plot reveals a possible dilution trend, as shown by other is widely used in high enthalpy (T N 150 C) and convergent margin
thermal springs in the Asal geothermal eld (Fig. 6). Moreover, in systems. However, in low enthalpy (T b 150 C) and basaltic rift sys-
these diagrams it is evident how Sakalol springs are generated by a tems, the Giggenbach's square plot (Giggenbach, 1988; Giggenbach,
mixing between three end-members: meteoric water with low chloride 1995) may also give useful information related to secondary pro-
concentration (cluster 1), meteoric origin uids from the surrounding cesses that may affect water and rocks (Fig. 8). In the ternary dia-
grabens (T.A.D.D. eld and Hanl springs with approximatively gram (Fig. 7), Clusters 2, 3 and 4 from the SHGF and the Hanl
18O = b 1 and 2H b 10) and rift water with high chloride geothermal well (BFGUR, 1999) are partially equilibrated and more
concentration (Asal geothermal wells). The graben and rift components and more shifted towards full equilibrium, suggesting that chemical
appear to be interrelated because both could be inuenced by alluvial- geothermometers can be used with care to estimate geothermal res-
lacustrine evaporates resulting in convergent chloride shifts. For ervoir temperature (Fournier and Truesdell, 1973; Fournier and
examples, the Dobi graben is characterized by the presence of salt pan, Potter, 1979; Giggenbach, 1988). On the other hand, samples from
remnants of a larger lake that lled it about 2000 ya (Kebede et al., Cluster 1 and boreholes from the SHGF and the Hanl geothermal
2008; Williams, 2016). However, supposing that chloride in cluster C4 well, sampled during this study are more shifted towards the magne-
(Galiceela sample; Fig. 6) derive mainly from a deep uid, a contribution sium corner and thus has not equilibrated with local volcanic rocks.
of approximatively 7% from Asal geothermal water can be inferred; the In the square plot (Fig. 8), the same trend for SHGF samples is
remaining 93% is attributable mainly to a regional uids, whereas a shown as a vertical path which departs from an almost horizontal
fresh meteoric input should be dominant in the other clusters. line that joins a non-equilibrium curve for isochemical dissolution
of local basalts and a full equilibrium curve at 35 C (the mean local
4.4. Geothermometry air temperature). For example, warm and cold water from the
Obock borehole (not shown, Awaleh et al., 2015a) and samples
The Na/1000K/100Mg0.5 ternary plot of Giggenbach (1988) can from the Hanl geothermal well sampled in this study plot onto the
be used to discriminate mature waters, which have attained equilib- horizontal line, suggesting that they are not useful for cation
rium with relevant hydrothermal minerals, from immature waters geothermometry. On the contrary, and according to Giggenbach
and waters affected by mixing and/or re-equilibration along their (1988), the vertical path should suggest that mixing occurred
circulation path, providing indications of the suitability of the waters between shallow and deeper aquifer and that the Na-K
Na/1000
Abhe
160 140
full equilibrium
200 100
#69
Allallobeda
Asal Hanl
#58
300 Tendaho
Dobi
partial equilibrium
160 140
200
immature waters
#35
AC AB
K/100 Mg
well-borehole BFGUR 1999

Hanl
Cluster 1
geothermal Houssein et al. 2010
Sakalol Cluster 2 wells
this study
Cluster 3
Cluster 4
Dobi waters with Cl > 1 g/l
seawater
Fig. 7. Trilinear geothermal diagram (samples data in mg/l; Giggenbach, 1988). AC and AB: isochemical dissolution of average crust and basalt, respectively (Giggenbach, 1988).
Temperatures of full equilibrium and immature waters/partial equilibrium curve are in degrees Celsius (C). The Dobi graben springs for Cl N1 g/l have been specied (triangles).
Samples data as in Fig. 3.
seawater Lake Asal

1.0
20
Isochemical
0.9 40
Basaltic Dissolution
Obock
tMg-Ca Trap
0.8 #35 Acid Tuff

Basaltic
Lava
60
0.7 Agna
#36
10Mg/(10Mg+Ca)
0.6
Full
Rhyolite
Equilibri
80
0.5
um
Minkileh
0.4
Dobi
100
0.3
tMg-Ca
Danab
0.2 120
tK-Na
Tendaho
Oued-Kalou
140
160 320 340
0.1 200 240 280
180 300
Abhe Allalobeda 220 260
Asal
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
10K/(10K+Na)
waters rocks
this study literature
borehole geothermal well

Asal
hot spring Dahla Basalts
Cluster 1 (Gasse 1987)
Sakalol Cluster 2 geothermal well Asal Basalts
(Pinzuti et al. 2003)
Cluster 3 Hanl borehole
Various Type
Cluster 4 hot spring
(Bosch et al. 1977)
Dobi water with Cl > 1 g/l
Fig. 8. Square geothermal diagram (samples data in mg/l; Giggenbach, 1988). Water samples data as in Fig. 3.
geothermometer (tNa-K on Fig. 8) could give more coherent results in with sulfates (Fig. 8). Therefore, in the following paragraph, classical
comparison with geothermometers that use Ca and Mg ions (tCa-Mg and new chemical and isotope geothermometers were used and
on Fig. 8). Indeed, minor horizontal and vertical shifting along the compared in order to obtain the best estimation of the reservoir tem-
vertical path is probably due to water re-equilibration at more perature of the SHGF.
supergenic conditions. This is conrmed plotting the SHGF samples
in activity diagrams which testify equilibrium with zeolites 4.4.1. Chemical geothermometers
(Fig. 9a), clays (smectites as saponites and montmorillonites) and/ The Na-K geothermometer is related to the variation of sodium and
or carbonates (Fig. 9b). The SHGF samples pertaining to the different potassium in thermal waters due to ion exchange of these elements be-
clusters are more and more shifted along the vertical path and to- tween coexisting alkali feldspars (e.g. Nicholson, 1993). The NaK
wards the full equilibrium curve, on which Cluster 4 samples geothermometer of Giggenbach (1988), based on thermodynamic
(Galiceela spring) fall quite close to the 160 C temperature point data for albite and K-feldspar, gives an equilibrium temperature of
(Figs. 7 and 8). However, it should be noted that the equilibrium deep parent uids of about 132184 C (Supporting information le).
curve represents a re-crystallization of a mean crustal rock from out- Furthermore, the NaK geothermometers of Fournier (1979) and
dated thermodynamic data (Giggenbach, 1988; Cortecci et al., 2005). Arnrsson et al. (1983) estimated the temperature of the geothermal
Moreover, the position over to the equilibrium curve on the square reservoir respectively at about 117173 C and 117168 C (Supporting
plot in comparison with the ternary geothermometric diagram information le). These temperatures agree with those obtained with
representing the Djibouti (Abhe, Hanl, Sakalol-Harralol and Asal) NaKCa geothermometer: 130168 C (Supporting information le).
and Dobi graben (Cl N 1 g/l) hot waters could testify to the addition Despite this agreement, it should be noted that most of the alkali
of calcium ion from secondary minerals, for example by interaction geothermometers could not give precise results because they are
6.0 e
lin ite basalt-seawater and Cl N 0.3 M equations give mean values lower than
oc s
without Na-heulandite icr illip e te the major cations geothermometers: 112 71 C (median 89 C) and
25C m h lin di
with Na-heulandite
a -p oc lan
N icr heu 107 49 C (median 92 C), respectively. The negative results obtained
without Na-heulandite i t e m -
ps Na ite
5.5
80C with Na-heulandite e illi
sit ph ps by the rst equation and the higher temperature obtained by other two
illi ite
llip Na- h nd
p h i -p la could be due to the combined effects of mixing and re-equilibration
K-
K
h eu
-
Na with clay minerals (as testied by activity diagrams, Fig. 9). In particular,
5.0
clay adsorption could be particularly effective for the lithium concentra-
tion, Li being a trace element. A temperature of 174 C was obtained for
the Galiceela springs by the Cl N 0.3 M equation. Considering the rela-
log[K /H ]
+
tively high lithium and chloride concentrations of this water and the un-
+
4.5
K-beidellite #90
certainty of 20 C related to these geothermometers (Sanjuan et al.,
2014), this results should be considered more reliable than that obtain-
ed for other springs.
4.0 Among several existing silica geothermometers, those proposed by
Fournier (1977) for quartz, and that of Arnrsson et al. (1983) for chal-
Na-beidellite cedony, have been used successfully both for alkaline thermal waters
3.5 and waters with T b 180 C (Michard and Beaucaire, 1993; Marques
et al., 2003; Asta et al., 2012; Fournier, 1991). This agrees with the su-
persaturation state of the studied waters with respect to those minerals:
3.0
A 0.56 0.13 for chalcedony and 0.82 0.13 for quartz (see supporting
5.0 5.5 6.0 6.5 7.0 7.5 information). Therefore, only chalcedony and quartz have been chosen
+ +
log[Na /H ] as silica geothermometers. In the present study, the quartz
14.0
geothermometers of Verma (2001) estimate the temperature of the
carbonates SHGF geothermal reservoir in the range of 111148 C, about 3 higher
e
25C sit s
silicates
ne -di than Fournier's equations and mean temperature between 133136 C
ag te
13.5 carbonates m mi e (Supporting information le). On the other hand, the reservoir temper-
80C lo it
silicates do calc
ature values estimated by the chalcedony geothermometers are in the
13.0 range 94127 C (Supporting information le). It should be noted that
most of the waters sampled are grouped between the chalcedony and
amorphous silica equilibrium lines (Fig. 10). In particular, some bore-
12.5 Mg-saponite
hole waters at the SHGF showed high dissolved silica concentrations
log[Mg /(H ) ]
+ 2
Ca-saponite (~ 100 mg/l) and plot near to the amorphous silica saturation at low
12.0 temperature. However, globally the waters studied are undersatured
2+
with respect to amorphous silica (SI = 0.29 0.09; see supporting

Mg-montmor information) and their outlined path suggests mixing with the local
11.5 e
sit is and shallow groundwater after a conductive cooling (Fig. 10). Also for
ne -d
ag ite silica, the highest temperatures of 148149 C were obtained for the
m om
l te Ca-montmor
11.0 do lci Galiceela sample, which suffered less cooling and mixing. For the
ca
same spring, temperatures of 152 C and 158 C were obtained by two
scolecite
equations calculated from the results of a leaching experiment per-
10.5
#90
formed on local basalts (trap and lava; Bosch et al., 1977):
kaolinite
B
10.0
10.5 11.0 11.5 12.0 12.5 13.0 13.5 14.0 T Cbasaltic trap 1576:085=logC5:799273 1
2+ + 2
log[Ca /(H ) ]
Fig. 9. Na-K (A) and Ca-Mg (B) activity diagrams. The Geochemist's Workbench (Bethke T Cbasaltic lava 2070:977=logC6:894273 2
and Yeakel, 2008) along with Thermoddem (release 2014; Blanc et al., 2012) and thermo.
com.v8.dat (B) thermodynamic datasets have been used to draw the solid phase limits in
diagrams (A) and (B), respectively. Activity of the dissolved species was calculated by where C = SiO2 in mg/l.
PHREEQCI (Parkhurst and Appelo, 2013). Temperatures by a pure thermodynamic approach were estimated
using PREEQCI and the full composition of the Galiceela samples. The ac-
tivity of the dissolved species of this latter was recalculated at specic
temperature up to quartz saturation. This was obtained at 151 1 C,
calibrated more than 30 years ago, that is using thermodynamic data to which is consistent with the result obtained from the basaltic trap
be updated (Cortecci et al., 2005). Therefore, as a rst approach, it would equation. At that temperature, the new activity of sodium and potassi-
be better to choose more recently calibrated equations or pure thermo- um was used to calculate the temperature of equilibrium between the
dynamic data (i.e. mineral solubility product and activity of dissolved alkali feldspars:
species) by using updated datasets. In fact, for the Galiceela sample
(#90), the value of 146 C obtained using the Na-K equation of Verma
albitelow K Kfeldspar Na
and Santoyo (1997) is 12 C lower than Giggenbachs one (160 C, as
also is estimable from Fig. 8) but more similar to that of 145 C obtained The logK of this reaction was calculated by using Rxn tool of The
by Na-K-Ca geothermometer (Supporting information le). Geochemists Workbench 7.0.6 software, version 7.0.6, and thermo.dat
Several Na-Li geothermometers have recently been proposed and/or
recalibrated (Sanjuan et al., 2014). However, what should be the most
appropriate for our samples (Cl b 0.3 M, equation 7 in Sanjuan et al., logK 3:4620:0194 T 6:449e5 T2 1:214e7 T3
2014) is unproductive because it gives negative results, whereas 9:581e11 T4 3
mean local air

temperature (35 C)
140
a
A2 C1
ilic
Abhe-1
ss
Dobi
hou
conductive
120 cooling
orp
Minkileh Q3
am
A1
100
Abhe-2
A3
80
SiO2 (mg/l)
60 B1 B2
y
on Q1
ed
lts
alc
sa
ch z
art
ba
40
qu
Q2
20
C2
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
Temperature (C)
well-borehole
Cluster 1
Asal geothermal well
Sakalol Cluster 2 Hanl
hot spring springs
Cluster 3
Cluster 4
Fig. 10. Dissolved silica vs. temperature. Sakalol data (diamonds) from this study. Asal (circles) and Hanl (squares) from the literature (see Fig. 3 for references). Squares with sharp edges
are Hanl data from this study. Curves represent the solubility of the different polymorphs: amorphous silica A1 (Verma, 2001), A2 (Fournier, 1977), A3 (Gunnarsson and Arnrsson,
2000); chalcedony C1 (Fournier, 1977), C2 (Arnrsson et al., 1983); quartz Q1 (Verma, 2001), Q2 (no steam loss, Fournier, 1977), Q3 (steam loss, Fournier, 1977). Equation describing
the silica obtained from dissolution at different temperature of local trap and lava basalts (B1 and B2, respectively) have been calculated from the data of Bosch et al. (1977). Means
and standard deviations for waters from Abhe 1 and 2 (small and great hydrothermal chimneys, respectively; Awaleh et al., 2015b) and the Dobi graben (Ali, 2005; UNDP, United
National Development Program, 1973) are also shown for comparison.
or thermo.com.v8.r6+.dat database 4.5. Dissolved sulfate: origin traced by isotope
The SO4/Cl vs SO4 plot is very useful to trace sulfate origin and its fate
logK 3:4890:01952 T 6:602e5 T2 1:303e7 T3 in groundwater (e.g. Kehew, 2001). In Fig. 11 C1 to C2 samples increase
1:138e10 T4 4 concentration with decreasing SO4/Cl ratios, which is the opposite be-
havior of solid sulfate dissolution. Moreover, and similarly to that of
the anion ternary plot, the position of some C1 and C2 springs in the di-
In the equations above, log K = log[Na+] log[K+], where square agram depicts the evolution path towards the Galiceela spring (C4
parentheses are the activity of the specie obtained from PHREEQCI, group; Fig. 11). However, the increase of sulfate concentration is in ac-
and the temperature in degree Celsius. cordance with the evolution of the mean gypsum/anhydrite saturation
Eq. (3) gives a temperature of 134141 C, whereas the equation indices of the SHGF cluster groups (an half of C2 samples and almost
Eq. (4) 137144 C. Therefore, a temperature range of 143 13 C all C3 samples fall near sulfate dissolution at 143 C and constant Na-
would be more realistic for the deep SHGF reservoir. Cl concentration; Fig. 11), whereas the decreasing SO4/Cl ratio testies
It is interesting to note the compositional transition of the Dobi gra- to a deep chloride input. In particular, and in correspondence with the
ben springs with Cl N 1 g/l: were similar to the Allalobeda waters during anhydrite saturation point at the mean deep temperature of 143 C, al-
rst analysis (UNDP, United National Development Program, 1973) most vertical trends (constant sulfate concentration and variable SO4/Cl
and then (Ali, 2005, 2011; Panichi, 1995) progressively to Abhe- ratios) are revealed also in hot springs from neighboring systems. For
Sakalol-Hanl reservoir (Fig. 8). Such a change was probably related to example, springs from the Hanl plain show increasing SO4/Cl ratios
an earthquake sequences (Noir et al., 1997) which enhanced permeabil- departing from Allallobeda-Abhe-Dobi mean values. This result is in
ity and the communication between uids at the Ethiopia-Djibouti agreement with the suggestion of a meteoric input from shallow sedi-
border. mentary formations (SO4/Cl up to 3 meq/l; data from Houssein
0.6
bicarbonate waters
interacting with
sedimentary formations
0.5
0.4
Minkileh
SO4 / Cl (meq/l)
gypsum
saturation
0.3
-
2-
Allallob.
Agna
sulfate dissolution
Dobi (143 C)
0.2
Abhe
meteoric
Danab input
anhydrite
0.1 seawater
sulfate dissolution saturation
(25 C) Tendaho Obock
#75
marine(?)
input
0
10 100 1000 10000
2-
SO4 (mg/l)

well-borehole
geothermal well
Cluster 1 geothermal well
Asal Hanl borehole
Cluster 2 Oued-Kalou
Sakalol hot springs hot-warm-cold springs
Cluster 3
Cluster 4 Dobi Cl > 1 g/l waters
Fig. 11. Sulfate/chloride ratio vs. sulfate concentration. Dotted curves represent calcium sulfate dissolution at different chloride concentrations (average of C1 and C2 clusters) and
temperatures, that is Cl = 15 mmol/kg H2O T = 25 C and Cl = 62 mmol/kg H2O T = 143 C, respectively. Bricked eld represent bicarbonate water interacting with sedimentary
formation in the Hanl graben (see Fig. 4). Mean standard deviation of waters from other geothermal elds in the Afar is also shown for comparison (see the Fig. 3 caption and
main text for references).
(2010). In a similar way: i) deep and shallow borehole waters from support to the second hypothesis, it should be noted that the sulfur iso-
Hanl are grouped on the low temperature gypsum dissolution curve; tope composition for dissolved sulfate at Galiceela (+11.4) is not dif-
ii) Oued-Kalou springs waters at Asal show high SO4/Cl ratios and ferent from the mean value for the SHGF springs waters (+ 11.4
group near to Dobi and Abhe mean values when meteoric input is 0.6) and very different from marine sulfate (+21). In Fig. 12a, it is
high, whereas the ratio is lowered and merge to the values of the Asal evident that most of the sampled waters are grouped near the 34S-
geothermal wells when a marine input prevails. A similar deep input enriched component represented by the solid and dissolved sulfate
of marine origin, i.e. a recycled seawater in the Asal rift geothermal from the Asal geothermal area (11.4 b 34S b 16.6; Fouillac et al.,
system, could be deduced for Galiceela samples, which fall near to the 1989; Gasse and Fontes, 1989). A closer look at the samples' distribution
back-extrapolation curve of the Obock samples. Alternatively, solid sul- in Fig. 12a reveals also that: i) 34S enriched component has a more re-
fate dissolution is enhanced by a high chloride content due to interac- stricted range of 11 b 34S b 14, this latter is comparable with sulfate
tion with evaporitic minerals, as is taking place for the Dobi graben from Lake Abhe hot springs waters (Awaleh et al., 2015b); ii) fresh wa-
samples with a relatively high chloride concentration (Fig. 11). In ters of Cluster 1 are more shifted towards a line joining Abhe springs
Lake Asal
18
17
A
16
S(SO4 ) ( vs. V-CDT)

15
14
13
2-
12
11
34
10
Oued-Kalou #75
9
#35
8
0 2 4 6 8 10 12 14 16 18 20
2- 3
(1/SO4 ) x 10 (mg/l)
this work literature
well-borehole Abhe
(hot springs)
Cluster 1
Cluster 2 Asal Rift
Cluster 3 (solid and dissolved sulfates)
Cluster 4
Asal hot springs
18
30
0C
17 B
250C
16
.5
15
=0
14
2
O
200
O(SO2-4 ) ( vs. V-SMOW)
2 /S
x10 -4
13 350
HS
C
C
12
O2 = 1
11
H2 S/S
10
9
40 #75
8 0C
O =1
H 2S/S 2 Lake Asal
7 #35
6
18
5
4
3
2
1
sulde oxidation
0
0 2 4 6 8 10 12 14 16 18
34 2-
S(SO4 ) ( vs. V-CDT)
Fig. 12. Sulfur isotope vs. sulfate concentration (A) and oxygen vs. sulfur isotope composition of dissolved sulfate (B). In both diagrams, solid and dissolved sulfate data from Asal Rift
basalts (gray eld) and Lake Asal are from Fontes et al. (1979), Fouillac et al. (1989) and Gasse and Fontes (1989). Dashed lines depict possible mixing or evolutive trends. In (B), the
grid represents sulfate composition after disproportionation of local magmatic SO2 (see text for details).
waters and a 34S-depleted component (34S b 11), represented by the Gypsum mounds analyzed in the Asal Rift showed values of 1.08 b
Dora borehole water (#35); iii) value of 34S N 16.6 are typically found 34
S b 16.3, which were interpreted as due to disproportionation of
where a seawater intrusion prevails (e.g. Manda spring or Lake Asal, magmatic SO2 but not veried by calculation (Moussa et al., 2016).
both in the Asal Rift area; Fontes et al., 1979; Gasse and Fontes, 1989). Fig. 12b helps verify this hypothesis and to better understand the sulfate
source in the aquifer in the SHGF. The Asal sulfate eld intercepts a grid The low temperature high 34S low 18O couple agrees with the value
that represents the isotope effect due to SO2 disproportionation at measured in the surface basalts and gypsiferous deposits at Asal
200350 C. The grid was calculated using a similar approach to that of (Fouillac et al., 1989; Gasse and Fontes, 1989). All Sakalol water samples
Rye et al. (1992), but using the disproportionation model and of this study fall within the grid and most of them near the Asal eld.
103ln(SO2 0
4 -S ) equation of Kusakabe et al. (2000) and mean values Therefore, we suppose that water samples at the SHGF acquired a
for 103ln(SO24 -H2S) obtained from Sakai (1968), Robinson (1973) disproportionated magmatic sulfate similar to those of the Asal area
and Ohmoto and Lasaga (1982). A primary magmatic value of interacting with sulfate minerals which may be included in the basaltic
34S(S) = 2.78 (Allard, 1979) was maintained for all calculations, rocks, fumarolic condensates or recycled in sedimentary phases. Suppos-
whereas the H2S/SO2 ratio was varied from 1 104, typical of the edly dissolved or deposited sulfates, whose values fall out of the grid,
Asal magmatic gas (Allard, 1979) up to 1 in accordance with the SO2 have an origin different from SO2-disproportionation of magmatic gas.
switch to H2S and SO24 during disproportionation and/or H2S/SO2 For example, in Fig. 12 this is the case for Asal sulfates with 34S N 17
ratio increase at near surface conditions (e.g. Kusakabe et al., 2000; and 18O b 9 which were inuenced by Holocene seawater (e.g. Lake
Wallace and Edmonds, 2011). At the same time, to simulate this transi- Asal; Fontes et al., 1979; Gasse and Fontes, 1989). On the other hand,
tion during the modeling calculation, the water isotope composition was and according to the sulfur general model at SHGF, the Cluster 1 and
gradually changed from 18O(H2O) = +6.0 (according to the basaltic the Dora borehole waters were more subjected to the oxidation of sul-
composition of the magmatic source; Fig. 5) to 18O(H2O) = +0.33 phide driven by atmospheric oxygen, this latter coming from fresh basalt
(mean value of the Asal geothermal water; Correia et al., 1985; and/or endogenous gas (i.e., in a similar way to that of steam-heated wa-
D'Amore et al., 1998). The comparison between the grid obtained, Asal ters; Boschetti et al., 2003; Bayon and Ferrer, 2005).
eld and SHGF samples of this study reveals some common features Finally, in Fig. 13, the temperature and SO4-H2O isotope fraction-
(Fig. 12b). The coupled low 34S - high 18O values of the Asal sulfate ation factors of the SHGF springs waters and deep source are compared
eld agree with a SO2-disproportionation at 250300 C, according to to theoretical equilibrium fractionation and the literature data for Abhe
the temperature of the deep reservoir (D'Amore et al., 1998). The high (Awaleh et al., 2015b) and Hanl (Aquater, 1986) springs. Samples dis-
temperature low 34S - high 18O couple of the Asal eld agree with the tributions conrm common water and sulfate sources. Despite similar-
values measured in the deep basalt and with the 34S of the hot springs ity of the temperatures in the Hanl-SHFG system and the M.E.R.
from the Asal geothermal area (Bosch et al., 1977; Fouillac et al., 1989). (Craig et al., 1977), these latter show lower oxygen fractionation values
mainly due to higher 18O(H2O), as shown in the water isotope diagram
(Fig. 5). Unfortunately, sulfate isotopes data for waters and minerals
from the Dora graben are not available.
Temperature (C)
4.6. Halogens (F, Cl, Br), boron and 11B/10B ratio
0
40
80
28
24
20
16
12
18
Like in other waters of the so called Fluoride Belt of the East African
#90
16 Rift (Gupta and Ayoob, 2016), the mean uoride concentration of
Sakalol reservoir
(143 C) Abhe 4.13 1.70 mg/l in the spring waters of the SHGF is higher than the
14
hot Lake 1.5 mg/l concentration limit for drinking water (WHO, World Health
12
springs Asal Organization, 2011). The SHGF mean value is higher than that for the
#75 Tendaho-Allallobeda waters, similar to that for the Dobi graben and
O
10 Asal waters, lower than the concentration shown for M.E.R. hot springs
2
-H
O
10 ln
2
4
(28.4 25.6 mg/l; Rango et al., 2013) and much lower than those for
-H
SO
-
8
4
Ca
the geothermal waters in that area (e.g. 71 17 mg/l in the Aluto-

3
HS
O
2
2- -H
4 #35 Langano Geothermal Field; Teklemariam and Beyene, 2001) which are
6 SO
M.E.R. Na-bicarbonate waters (Fig. 14a). The cause of the high concentration
4 in M.E.R. waters was related to low calcium concentration in solutions
2
and interaction with uorite, which could be present in sedimentary
Allalobeda
(7995 C)
and volcanic formation and is more soluble than other uoride-
0 bearing minerals (Gizaw, 1996; Garca and Borgnino, 2015). Calculated
saturation indices show uorite undersaturation for SHGF springs with
-2
3 4 5 6 7 8 9 10 11 12 a very high standard deviation: 1.32 1.13. The reason for this high
6 2
10 /T (kelvin) scatter is probably also the cause of the different concentrations from
those of the M.E.R. hot waters, that is the simultaneous dissolution of
this study
calcium sulfate minerals which cause uorite precipitation due to a
literature
common-ion effect (e.g. Appelo and Postma, 2007). Scattering is higher
well-borehole in the diluted waters of the SHGF C1 cluster and is as also shown by the
Cluster 1
Sakalol Cluster 2
Hanl springs
(Aquater 1986)
Hanl geothermal wells. Fluorine concentrations are due to interaction
Cluster 3 with sediments or volcanic ash or scoria of the shallow and recent for-
Cluster 4 mations (e.g. Ghiglieri et al., 2012).
Unlike uoride, boron isotopes are good geochemical tracers be-
cause of the high mobility of this element during water-rock interaction
Fig. 13. Sulfate-water oxygen isotope fractionation as 103ln () vs. temperature (Kelvin
processes (Hoefs, 2015). Boron is preferentially hosted in
and Celsius) for Sakalol springs (diamonds; this study). Full equilibrium lines are shown
(see Boschetti, 2013 for equations). Like Abhe deep geothermal water (Awaleh et al., phyllosilicates, whereas the B concentrations of common mantle and
2015b), the temperature obtained by chemical geothermometers for Galiceela hot crustal minerals (except tourmaline) are low. The low boron concentra-
spring (#90) is compatible with an oxygen isotope equilibration between anhydrite and tions of the Tadjourah Gulf basalts (0.20.8 ppm and 4 15 11B;
water. Data from M.E.R. hot springs, with focus on Allalobeda (mean standard Chaussidon and Marty, 1995) conrm this theory. B versus Cl and 11B
deviation, UNDP, United National Development Program, 1973); Abhe (Awaleh et al.,
2015b) and Hanl (Aquater, 1986; squares) spring waters are also shown for
versus Cl/B are useful diagrams for the study of geothermal systems
comparison. The vertical dashed line represents mean local air temperature (T = 35 C), (Aggarwal et al., 2000; Bernard-Romero et al., 2010; YuanYuan et al.,
but arrows possible mixing or evolutive trends. 2014). To the best of our knowledge there are no published 11B data
Cl (mg/l)
10 100 1000 10000 100000
10
M.E.R. hot springs: (F = 28.5 25.6 mg/l)
M.E.R. groundwaters (Rango et al. 2013)
9
(Rango et al. 2013)
6
F (mg/l)
4
Dobi
2
WHO (2011) Allallobeda
seawater
Abhe
F limit in groundwater
1 Tendaho Obock
0
#35 A
10
M.E.R. geothermal waters
9
(Aluto-Langano)
6
M.E.R. hot springs
B (mg/l)
seawater
(Rango et al. 2013)
5
Tendaho
Obock
4
3 Abhe
Allallobeda
basalts
2
Asal
Dobi
(fum. condensate)
1 #35
0
B
10 M.E.R. groundwaters 100 1000 10000 100000
(Rango et al. 2013) Cl (mg/l)

geothermal well
Asal
well-borehole hot spring
Cluster 1
geothermal well
Sakalol Cluster 2
Hanl borehole
Cluster 3
hot spring
Cluster 4
Dobi Cl > 1 g/l waters
Fig. 14. Chloride concentration vs uoride (A) and boron (B) concentrations. Literature data sources as in Fig. 3. In (B) basalts curves represent typical B/Cl ratio in basaltic rocks
(Arnrsson and Andresdottir, 1995; Reyes and Vickridge, 1996), which are similar in Aluto-Langano geothermal waters from the M.E.R. (Gianelli and Teklemariam, 1993; Teklemariam
and Beyene, 2001). Dashed, dotted and dash-dot depict Asal-Tendaho, seawater-meteoric and Asal geothermal water Asal fumarole (Virkir-Orkint, 1990) binary mixing lines. In both,
the arrow depicts a possible evolutive trend for Sakalol hot spring waters.
for geothermal waters in the African Rift at the time of writing. In boron concentration of most Cluster 3 and Cluster 4 (Galiceela) waters
Fig. 14b, it is evident that the boron concentration increases from Clus- were relatively high compared to Cluster 1 waters and more shifted to-
ter 1 to Cluster 4, like in other Afar rift hot waters. In particular, the wards seawater-derived uids such as Asal or Obock. This is also
45
A marine source
35
Asal geothermal reservoir

B ( vs SRM951)
25
Lake Asal
15
5 d
lan
11
ice
-5
non-marine
source
basalts
-15
1 10 100 1000 10000
Cl/B (mg/l)

well-borehole geothermal well
Asal
Sakalol Cluster 2
geothermal well
Cluster 3
Hanl borehole
0.1
hydrothermal
B
#35
basalts
Allallobeda
0.01 Abhe
Danab
sewage
B/Cl (mol)
Dobi
seawater
evaporation
0.001
agriculture drainage #74
evaporites seawater
Lake
intrusion
Asal
0.0001
0.0001 0.001 0.01
Br/Cl (mol)
Fig. 15. Br/Cl vs B/Cl (A) and Cl/B vs 11B (B). In (A), elds represent different geothermal waters worldwide from Aggarwal et al. (2000), Bernard-Romero et al. (2010) and YuanYuan et al.
(2014). Exception is provided by the Lake Asal and Asal geothermal reservoir elds, whose Cl/B ratios only are shown (Bosch et al., 1977; D'Amore et al., 1998; Sanjuan et al., 1990) because
boron isotope ratios are not available. The basalt eld data was adapted to local rocks for isotope ratio (Chaussidon and Marty, 1995) and Cl/B ratio from literature data (see text and B vs. Cl
plot). In (B), elds and paths are from Vengosh (2014), except basalt (Arnrsson and Andresdottir, 1995; Mller et al., 2016). See Fig. 3 for the references on the sample data from Djibouti
(Abhe, Asal, Hanl) and the Ethiopian Afar (Allalobeda, Danab, Dobi). In (B), elds represent different geothermal waters worldwide (Aggarwal et al., 2000; Bernard-Romero et al., 2010;
YuanYuan et al., 2014).
conrmed by higher ratio Cl/B ratios of the SHGF (median = 853 mg/l) of a uid similar to the Asal geothermal uid in the SHGF geothermal
than those of the hot springs and geothermal wells from M.E.R., these circuit. Taking into account the involvement of seawater in the Asal geo-
latter ratios are more similar to the low Cl/B typical of basalts (30120 thermal system (D'Amore et al., 1998), the assumption of one hypothe-
by weight, Fig. 14b; Arnrsson and Andresdottir, 1995; Reyes and sis does not exclude the other. In fact, in spite of the different boron
Vickridge, 1996). As shown in Fig. 15, this could be interpreted in sever- concentrations in clusters, all samples are shifted towards a marine or
al ways such as a seawater origin for these elements or an involvement a geothermal-marine source. The relatively high 11B value for the
SHGF waters could be due: i) B delivered by gas, but this should be a 4.7. Strontium and carbon isotopes
very minor contribution, considering the low concentration of boron
in Asal and Hanl fumaroles (Aquater, 1986; Virkir-Orkint, 1990); ii) The 87Sr/86Sr ratio determined in water reects the distinct isotope
boron fractionation due to preferential inclusion of 10B in carbonate composition of the interacting rocks (Goldstein and Jacobsen, 1987;
and clay minerals (e.g. Hemming et al., 1995). This hypothesis is more Drever, 1997). Few water 87Sr/86Sr data are available for Djibouti
probable considering the equilibrium or slight supersaturation with re- (Sanjuan et al., 1990; Dekov et al., 2014; Awaleh et al., 2015b; Awaleh
spect to aragonite and calcite, respectively, and the clay-zeolites activity et al., 2016). The ratios of the investigated water samples range from
diagrams (Fig. 9). The probable secondary fractionation effects and the 0.70365 to 0.70626 (Table 2). This data is compared with the 87Sr/86Sr
lack of 11B data for the surroundings geothermal reservoirs (e.g. Asal, values of local lithotypes and waters available in the literature in order
Abhe, Hanl, Dobi) which may hide some informations, the use of a to dene the nature of the interacting rocks and possible relationships
more discriminating diagram such as Br/Cl vs B/Cl on a molar basis (Fig. 16). Sr isotope values for basalt samples from the Republic of
(Shikazono, 2003; Vengosh, 2014) could be useful (Fig. 15). Most of Djibouti show a considerable variation from 0.70309 to 0.70664,
the samples from the SHGF are grouped within or in the low right cor- where the higher values correspond to older rocks (10 to 25 My) that
ner of the hydrothermal eld suggested by Vengosh (2014). Abhe, included a subcontinental lithospheric component (Barrat et al., 1993;
Dobi and Allallobeda geothermal waters depart from this eld, but Clus- Deniel et al., 1994; Faure, 2001; Vidal et al., 1991).
ter 1 follows the grouping depicted by the mean and standard deviation The relatively low 87Sr/86Sr ratio (0.70365; Table 2) observed in C4
values, suggesting that the right limit for a hydrothermal eld should be thermal waters indicates that Sr is predominantly leached from the un-
extended slightly. This is also conrmed by the results for the Dora sam- derlying volcanic rocks, most likely from the Stratoid Series that domi-
ple, which falls within the ratios values for basalts (Br/Cl = 0.0013 to nates the bedrock in the Southwestern region of the Republic of
0.0023 in Mller et al., 2016; B/Cl = 0.022 to 0.1 of alkali basalts in Djibouti (Vidal et al., 1991; Barrat et al., 1993). According to a shift to-
Arnrsson and Andresdottir, 1995). Finally, the rough linear trend wards the Sr isotope ratios of Quaternary Stratoid basalts (Fig. 16), the
87
shown by Clusters 2, 3 and 4 conrm the involvement in the SHGF of Sr/86Sr value for C4 thermal water from the SHGF is slightly lower
a geothermal water of marine origin, similar to the Asal geothermal than the Sr isotope value for Djibouti geothermal waters ranging from
water (Fig. 15). 0.703809 to 0.70463 (Awaleh et al., 2015b; Sanjuan et al., 1990). In a
87 86
Sr/ Sr
0.703 0.704 0.705 0.706 0.707 0.708 0.709 0.710
100
gs
sprin #35
in hot
orig
ric
10 eo
et
m
Abhe
alluvial/unconed
groundwaters
1 Oued-Kalou (Awaleh et al. 2016)
K2
Oued-Kalou
K1
1/Sr (mg/l)
seawater
0.1
Red-Sea brines
(Pierret et al. 2001)
Korili
ho t springs
e origin
a rin
0.01 m Lake Asal
Afar Dahla
Plume basalts
(0.70350) (0.70411)
0.001
Quaternary
Basalts
low-T travertine
(0.70366)
(Dekov et al. 2014)
0.0001

well-borehole
Cluster 1
geothermal well
Sakalol Cluster 2 Asal
hot spring
Cluster 3
Cluster 4
Fig. 16. 87Sr/86Sr vs. 1/Sr. Means and standard deviations for Djibouti basalts (Faure, 2001) and Abhe hot springs (Awaleh et al., 2015b) are shown for comparison. Curves represent binary
mixing of the hot waters in Sakalol (this study) and Asal (Sanjuan et al., 1990) which represents geothermal waters of meteoric and seawater origin. It is interesting to note that the Oued-
Kalou spring waters from Asal plot in the middle (dotted line is the best t for these springs), whereas Red sea brines (Pierret et al., 2001) plot between seawater and Lake Asal water
(Sanjuan et al., 1990). The dashed line encloses non-thermal groundwater samples from alluvial and Dahla basalt aquifers (Awaleh et al., 2016).
-
seawater H CO3 (mg/l)
0 100 200 300 400 500 600 700 800
Asal geothermal reservoir 0
(DAmore et al. 1988) Allallobeda
(Craig et al. 1977) Agna -2
mantle African-Rift
high-T springs M.E.R. hot springs
-4
C(DIC) ( vs V-PDB)
CO2 (Darling et al. 1996) (Bretzler et al. 2011)
-6
-8
Dora (#35)
Water-atmospheric CO2
equilibrium at 35C -10
water-silicate interaction -12

(open system)
13
#36 -14
rift-escarpment CO2
(Bretzler et al. 2011) low-T groundwater -16
A
-18
Minkileh
120
Sakalol water rift-escarpment CO2
(Fontes et al. 1980; Verhagen et al. 1991) (Bretzler et al. 2011) seawater
100
Abhe hot spring
C(DIC) (% mC)
80
Hanle hot spring
(Fontes et al. 1980) Dora (#35)
Agna 60
Asal hot spring
40
Djibouti groundwater M.E.R.
14
(Fontes et al. 1980; Verhagen et al. 1991)
20
wadi-recharged aquifers
(Fontes et al. 1980; Awaleh et al. 2015) B mantle CO2
0
-20 -15 -10 -5 0
13 13
local +8 > C > -5 (Gasse & Fontes 1989) C(DIC) ( vs V-PDB)
carbonate
minerals 13
-2 > C > -7 (Fouillac et al. 1989)
Fig. 17. Stable isotope carbon 13C(DIC) in relationship with carbonate alkalinity concentration as HCO 3 (A) and
14
C (B), respectively. Colored and open diamonds represent Sakalol waters
from this study (symbols as in Fig. 16) and the literature, respectively (Fontes et al., 1980; Verhagen et al., 1991). In (A), 13C values for local carbonate minerals are also shown and plotted
for HCO 3 60 mg/l resulting from water, CaCO3 and logPCO2 = 3 equilibrium at 50 C (calculated by the PHREEQCI program); dashed lines enclose non-thermal groundwater silicate
which has shown high HCO 13
3 and low soil C(DIC) due to silicate interaction in open-system condition and CO2 from soil (Clark, 2015; Awaleh et al., 2016), whereas arrows depict
possible mixing trends. Red curves depict the trend of the hot springs from the African Rift (Darling et al., 1996), with a CO2 contribution evolving from rift-escarpment to deep mantle
(Bretzler et al., 2011). Symbols and elds are the same as in (B) if available.
similar way, the Abhe and diluted Oued-Kalou hot spring waters, both The 13C(DIC) data from this study is generally more positive than pre-
interacting with Stratoid basalts, plot near to the evolutive model traced viously published data from the same area (Fig. 17a). This is in accor-
for the SHGF (Fig. 16). This is in agreement with the chemical and iso- dance with the suggestion of an inux of magmatic CO2, in particular
tope composition, in particular in terms of equilibration with rocks for C3 waters with a mean of 4.3 2, which is comparable with
and the distinction between meteoric and seawater recharge, respec- the mantle value of 4 2 (Bretzler et al., 2011; Darling, 2004;
tively. On the other hand, the Dora borehole non thermal groundwater Oppenheimer et al., 2014). Moreover, it should be noted that the
has the most radiogenic value (0.70626) of the study area (Table 2; SHGF waters show a low alkalinity value, more compatible with geo-
Fig. 16), which is within the range of the Sr isotope value thermal waters from the Afar such as Allallobeda waters (Craig et al.,
(0.705560.70694) of Djibouti volcanic aquifers groundwater (Awaleh 1977) rather than M.E.R. waters (Bretzler et al., 2011; Craig et al.,
et al., 2016). Therefore, the high 87Sr/86Sr ratios observed for the Dora 1977; Darling et al., 1996). In a similar way, 13C(CO2) in the Asal geo-
borehole groundwater was probably mainly related to the recharge of thermal wells waters showed values of 2.6 to 3.1 with null carbon-
the Dora volcanic aquifer by an alluvial-wadi aquifer as observed for ate alkalinity (D'Amore et al., 1998). Unexpectedly, C4 water shows
most of the Djibouti volcanic aquifers (Awaleh et al., 2016). C2 and C3 quite a low value for 13C(DIC) = 9.74 , probably due to a re-
thermal waters plot below the evolutive trend proposed for the SHGF equilibration at surface conditions after degassing, as testied by the
in the 87Sr/86Sr vs. 1/Sr plot (Fig. 16). This may be due to the non- calculated near atmospheric logPCO2 value of 3.4. Its calculated
conservative behavior of dissolved Sr, such as sorption, ion exchange, 13C(CO2) of 14.4 is compatible with a contamination by soil CO2,
or dissolution/precipitation reactions (Bretzler et al., 2011). For exam- as is more evident for the non-thermal well #36 water (18.9) and
ple, a diffused presence of hydrothermal calcite with a high Sr concen- previous-published data from the SHGF and Abhe (Fig. 17a; Fontes
tration in the study area could be an explanation. et al., 1980). Similar DIC value was observed for Dora non thermal
The isotope composition of dissolved inorganic carbon (13C/12C and water, which falls near to typical wadi-recharged water (Fig. 17a;
14
C) of the SHGF waters is interesting when compared with literature Verhagen et al., 1991).
data for Djibouti (Awaleh et al., 2016; Verhagen et al., 1991; Fontes In comparison to published 14C data for Djibouti thermal and non-
et al., 1980) and M.E.R. (Bretzler et al., 2011; Craig et al., 1977) waters. thermal groundwater, the 14C content of the SHGF waters is one of the
lowest observed in the country (25 5% pmc), which further conrms chalcedony equilibrium of C2C3 samples), and (ii) a deep geothermal
the inux of 14C-free mantle CO2 having 13C value between reservoir located about 20002500 m depth (T 143 C according to
2 6 (Fig. 17b). The 13C-14C plot (Fig. 17b) also reveals the pos- the temperature inferred from C4 sample).
sible effect of 13C enrichment due to (re)equilibration with local calcite, Based on the groundwater movements towards the SHGF, the re-
as also shown in Fig. 17a. Radiocarbon dating after a 14C correction by sults of geochemistry and isotope data, and the results of the recent geo-
Netpath XL gave a median value of 6.8 2.4 ka (see supporting infor- physical study on the SHGF, a conceptual model has been proposed for
mation le), which is quite comparable to the period of Asal-Sakalol hy- the SHGF (Fig. 18). It is of interest to note that groundwater recharged
drothermal connection (Gasse and Fontes, 1989). It is interesting to from the Moussa Ali Mountain can be tapped at about 150200 m
note that the age calculated for the most ancient C4 water dept as has been noticed in Dora area in the North of the SHGF. There-
(8.69.0 ka) is compatible with that predicted for the paleowater de- fore, it is likely that groundwater recharged from the Moussa Ali Moun-
tected in the Bara desert (Awaleh et al., 2016), whereas the lower values tain feed the intermediate geothermal reservoir of Sakalol-Harralol
detected for Cluster 2 and 3 (1.4 1.0 ka and 3.3 2.0 ka respectively) geothermal system (Fig. 18). However, only the feasibility study with
agree with the that of the ancient salt lake in the Dobi graben drilling geothermal wells and further isotope analysis of intercepted
(Williams, 2016). uids can make sure if the groundwater recharged from Moussa Ali
Mountain feed as well the deep geothermal reservoir of the SHGF.
4.8. Conceptual model of the SHGF: an attempted union of hydrological and The regional aquifer is recharged mainly from the Ethiopian high-
geochemical data light and end up in Djibouti (Gasse and Fontes, 1989). Furthermore, it
has been shown recently that the regional aquifer feed the geothermal
There is a few piezometric data in the region. However, the piezo- reservoir of Lake Abhe area, located on the south-west of the SHGF
metric map of the region, which has been adapted from the country pi- (Awaleh et al., 2015b). Additionally, the geothermal prefeasibility of
ezometric map (BGR, 1982), has shown clearly that groundwater Hanl area (located between Lake Abh area and SHGF), with one geo-
recharged from the Moussa Ali Mountain from the north of SHGF thermal well with a depth of about 2025 m, showed clearly that such a
ows towards the Sakalol-Harralol depressions (Fig. S4, see supporting regional aquifer (BFGUR, 1999): i) feeds as well the geothermal reser-
information). The piezometric map has shown as well that the regional voir of Hanl geothermal system; ii) can be tapped at about 200 m
aquifer groundwater, recharged from the Ethiopian highlights, ows to depth. On this basis, it is likely that the regional aquifer may feed the in-
the Sakalol-Harralol depressions (Fig. S4, see supporting information). termediate geothermal reservoir of Sakalol-Harralol system as well as
Moreover, our geochemical results have shown that Asal Rift uids the deep geothermal reservoir of SHGF (Fig. 18).
ow towards the SHGF. Our present study conrmed the prediction of the connection be-
On the other hand, it has been evidenced from geochemistry and iso- tween the Asal Rift uids and Sakalol-Harallol area (Gasse and Fontes,
tope data that thermal waters in the SHGF result from the mixing of 1989). Therefore, the Asal geothermal uids, which go through
three groundwater: (i) the regional aquifer groundwater; (ii) the paleochannel, are likely to feed the deep geothermal reservoir of the
groundwater recharged from the Moussa Ali Mountain; and (iii) the SHGF. However, only feasibility study with drilling geothermal wells
groundwater that ow from Hanl area to the Sakalol-Harralol depres- can make sure if this uid from Asal geothermal eld may feed as well
sions passing through the Asal Rift. the intermediate geothermal reservoir of the SHGF. Since the Asal Rift
Furthermore, a recent geophysical study (MT, TDEM, Gravimetry) system is recharged mainly by seawater and in some extend by meteor-
has shown the possible existence of two geothermal reservoirs in the ic water (SanJuan et al., 1990), the age of the Asal Rift uids that transit
SHGF (CERD, 2016): (i) an intermediate geothermal reservoir located to Sakalol-Harralol depressions (at about 9000 y BP) may be due to a
at about 300600 m depth (probably at T 110 C according to long transit rather than been fossil water.
SW NE
? (3)
(2) I
(T 110C) ?
II
(T 143C)
(1)
Heat source
Fig. 18. A simplied sketch of the conceptual model of the Sakalol-Harralol geothermal system. I: Intermediate geothermal reservoir (temperature inferred by chalcedony equilibrium of
the C2C3 clusters); II: Deep geothermal reservoir (temperature inferred from the C4 sample). (1) Meteoric waters that transit from Asal local rift to the Sakalol-Harralol depressions;
(2) The deep circulating regional aquifer; (3) Groundwater recharged from Moussa Ali Mountain.
The schematic section, depicted in Fig. 18, illustrates the possible type waters, while non-thermal groundwater or the freshest thermal
ow patterns of the SHGF. Therefore, the deep geothermal reservoir waters are mostly Na-Cl-HCO3-SO4 waters. The increase of salinity
may mainly been recharged by the regional aquifer groundwater and from Cluster 1 to Cluster 4 is due to a combination of contributions
the Asal Rift uids that transit from the Asal local rift to Sakalol- from evaporites, mainly evident in Cluster 3 and typical of the passive
Harralol depressions (Fig. 18). On the other hand, the intermediate geo- graben setting in the Afar, and a recycled seawater component of the
thermal reservoir may be feed by the groundwater recharged from the geothermal water of the active Asal rift, mainly evident in Cluster 4
Moussa Ali Mountain and in some extends by the regional aquifer (approximatively 7%). Those contributions are obliterated by progres-
(Fig. 18). During their ascent by convection through basalt fractures, sive equilibration with Stratoid basalt; however, the seawater imprint
the geothermal uids from the intermediate and the deep geothermal is particularly evident from the elevated values of boron isotopes and
reservoirs would mix together in varying degrees and in some extend the relatively high chloride concentration in comparison with more di-
with the deep circulating regional aquifer, after an additional mixing luted samples. On the contrary, and as expected in rift setting (Shanks
with groundwater recharged from Moussa Ali Mountain.. It is of interest et al., 1981; Awaleh et al., 2015a), no trace of seawater was revealed
to note that those groundwaters have similar residence time than those by the isotope composition of dissolved sulfate. Instead, a dominant
from basalt aquifers encountered in the republic of Djibouti (Awaleh contribution of sulfate derived from magmatic SO2 disproportionation,
et al., 2016). The low mineralization of C1 thermal water may be ex- which may take place locally in a different form (i.e. included in basalt
plained by the fact that the groundwater recharged from Moussa Ali rock, recycled in sedimentary evaporate, fumarolic condensate) was
Mountain is to some extend mixed with fresh shallow water during proven. Different contributions in term of water recharge spread the
its ascent. samples in terms of water isotope composition. Cluster 1, Cluster 4
and Clusters 23 are probably fed with meteoric water from Moussa
4.9. Prediction of the scaling Ali Mountain, meteoric water that transit from Asal local rift to
Sakalol-Harralol depression and meteoric water from the deep circulat-
All waters are undersaturated with respect to anhydrite, gypsum, ing regional aquifer respectively. This latter may be the result of differ-
uorite, halite and slightly oversaturated in calcite (see supporting in- ent, mixed contributions.
formations). In particular, water groups show a progressive increase of Locally, the deep geothermal reservoir may be recharged mainly
the mean sulfate minerals saturation indices, with no signicant distinc- by the regional aquifer groundwater and the Asal Rift uids that
tion between anhydrite and gypsum: C1 = 2.4 0.2; C2 = 1.9 transit to Sakalol-Harralol depressions. Whereas, the intermediate
0.2; C3 = 1.3 0.2. The Galiceela samples (C4) gave the highest geothermal reservoir may be feed by the groundwater recharged
values: SIgypsum = 0.69 and SIanhydrite = 0.39. from the Moussa Ali Mountain and in some extends the regional
The prediction of scaling tendencies of geothermal waters is impor- aquifer. During their ascent, the geothermal uids from the interme-
tant in evaluating the production characteristics of geothermal aquifers diate and the deep geothermal reservoirs would mix together and in
and for taking necessary precautions to prevent or control scale forma- some extend with the deep circulating regional aquifer, with an ad-
tion (Tarcan, 2005). In other words, the saturation indices (log Q/K) of ditional mixing with groundwater recharged from Moussa Ali
some carbonate, sulfate, and silica minerals may help one to estimate Mountain.
which ones of these minerals may precipitate during the extraction Different geothermometrical approaches give a temperature range
and utilization of the geothermal uids. Therefore, an assessment of estimates for the deep geothermal reservoir of approximatively
scaling tendencies may involve the calculation of the saturation state 120160 C, with a mean deep temperature of 143 C. According to pre-
of these scale-forming minerals. The saturation indices of these latter vious hydrological studies, it could be also likely the presence of a shal-
in the SHGF thermal waters were computed as a function of tempera- low aquifer at 110 C. Common features in terms of deep temperature,
ture. The carbonate minerals (calcite, aragonite, and dolomite) were chemical and water-isotope composition were revealed between the
found to be oversaturated at 50300 C in almost all thermal waters in Sakalol-Harralol deep geothermal water and the Hanl, Abhe, Dobi gra-
the SHGF with the exception of the hot springs Galiceela water (sample ben and diluted shallow aquifer waters of the Asal geothermal eld.
# 90) (Fig. S3, see supporting information). Therefore, carbonate min- Therefore, the so called regional aquifer may have a wider extension
erals will be most likely to precipitate as scales from the thermal waters than previously assumed. Finally, the results of geochemical studies
of SHGF during future geothermal production. Indeed, the precipitation and eld observation suggest that the most likely scales to be precipitat-
of carbonate minerals from geothermal spring waters in the SHGF is ed during the extraction of thermal water in the study area are carbon-
best illustrated by the occurrence of hydrothermal calcite edices, sev- ate minerals. Apart from being a step forward in the characterization of
eral meters high, in the vicinity of still active thermal springs (Fontes the geothermal resource of the Sakalol area and therefore bringing the
et al., 1979). This formation process is probably the same as that in key knowledge for an utilization of this renewable energy, this study
Lake Abhe (Fontes and Pouchan, 1975; Fontes et al., 1980; Dekov will serve as a valuable example of a large multi-tracer isotope and geo-
et al., 2014). chemical characterization of a complex geothermal system.
It is of interest to note that silicate scaling was observed in Asal geo-
thermal wells along with sulphides precipitations (Aquater, 1989;
D'Amore et al., 1998). Indeed, uids produced from Asal geothermal Acknowledgments
wells have shown strong scaling tendency related mainly to sphalerite
and galena precipitation in the production casing and silica precipita- This research work was nancially supported by the Centre d'Etudes
tion in wellhead (Aquater, 1989; D'Amore et al., 1998). However, car- et de Recherche de Djibouti (CERD). We are grateful to Abdillahi Elmi
bonate precipitation was not reported for Asal geothermal wells Adaneh, Ismael Said Ismael and Sikieh Abdillahi Elmi for their assistance
(Aquater, 1989). in the eld works. We would like to thank the Djibouti National Army
for their assistance in logistic. We would also like to thank two anony-
5. Conclusions mous reviewers for their constructive comments that improved the
manuscript.
Hot springs in the Sakalol-Harralol geothermal eld were found to
be aligned NW-SE along the main faults. Four groups of waters (Clusters Appendix A. Supplementary data
14) were dened using HCA and PCA and an excellent correspondence
was found with their geographical location. Alkaline thermal waters in Supplementary data to this article can be found online at http://dx.
the Sakalol-Harralol geothermal eld were found to be high TDS Na-Cl doi.org/10.1016/j.jvolgeores.2016.11.008.
References Bosch, B., Deschamps, J., Leleu, M., Lopoukhine, M., Marc, A., Vilbert, C., 1977. The geo-
thermal zone of Lake Assal (F.T.A.I.), Geochemical and experimental studies.
Geothermics 5:166175. http://dx.doi.org/10.1016/0375-6505(77)90017-7.
Aggarwal, J.K., Palmer, M.R., Bullen, T.D., Arnrsson, S., Ragnarsdttir, K.V., 2000. The Boschetti, T., 2011. Application of brine differentiation and LangelierLudwig plots to
boron isotope systematics of Icelandic geothermal waters: 1. Meteoric water charged fresh-to-brine waters from sedimentary basins: diagnostic potentials and limits.
systems. Geochim. Cosmochim. Acta 64:579585. http://dx.doi.org/10.1016/S0016- J. Geochem. Explor. 108:126130. http://dx.doi.org/10.1016/j.gexplo.2010.12.
7037(99)00300-2. 002.
Ali, S., 2005. Geochemical Studies of the Tendaho Geothermal Field. Proceeding World Boschetti, T., 2013. Oxygen isotope equilibrium in sulfate-water systems: a revision of
Geothermal Congress, Antalya, Turkey, April 2429. geothermometric applications in low-enthalpy systems. J. Geochem. Explor. 124:
Ali, S., 2011. Geochemistry of the Dubti Wells and the Alalobeda Hot Springs. Proceedings 92100. http://dx.doi.org/10.1016/j.gexplo.2012.08.011.
Kenya Geothermal Conference, Kenyatta International Conference Center, Nairobi, Boschetti, T., Cortecci, G., Bolognesi, L., 2003. Chemical and isotopic study of the shallow
November 2122. groundwater system of Vulcano Island, Aeolian Archipelago, Italy: an update.
Allard, P., 1979. 13C/12C and 34S/32S ratios in magmatic gases from ridge volcanism in Afar. GeoActa 2, 134.
Nature 282:5658. http://dx.doi.org/10.1038/282056a0. Bretzler, A., Osenbrck, K., Gloaguen, R., Ruprecht, J.S., Kebede, S., Stadler, S., 2011.
Allard, P., 1983. The Origin of Hydrogen, Carbon, Sulphur, Nitrogen and Rare Gases in Vol- Groundwater origin and ow dynamics in active rift systems a multi-isotope ap-
canic Exhalations: Evidence from Isotope Geochemistry. In: Tazieff, H., Sabroux, J.-C. proach in the Main Ethiopian Rift. J. Hydrol. 402:274289. http://dx.doi.org/10.
(Eds.), Forecasting Volcanic Events. Elsevier, pp. 337386. 1016/j.jhydrol.2011.03.022.
Appelo, C.A.J., Postma, D., 2007. Geochemistry, Groundwater and Pollution. second ed. A. BRGM, 1970. Reconnaissance gothermique du Territoire Franais des Afars et des Issas
A. Balkema, The Netherlands. (TFAI). Orlans, France, April 1970. BRGM/70-SGN-109GTM (59 pp.).
Aquater, 1986. Prfaisabilit gothermique de la Zone de Gaggade - Etudes CERD, 2016. Etude de prfaisabilit gothermique Rgion des Lac Alols Rpublique de
complmentaires. San Lorenzo in Campo, Italy, June 1986. AQUATER S.p.A. ISERST, Djibouti. Centre d'Etudes et de Recherche de Djibouti (CERD), Djibouti, Republic of
Republic of Djibouti (115 pp.). Djibouti (Octobre 2016. 78 pp.).
Aquater, 1989. Djibouti Geothermal Exploration Project. Final Report GEOTA3770/JOB Chaussidon, M., Marty, B., 1995. Primitive boron isotope composition of the mantle. Sci-
339400. San Lorenzo in Campo, Italy, August 1989. AQUATER S.p.A. INTAIRDRILL ence 269:383386. http://dx.doi.org/10.1126/science.269.5222.383.
Ltd ISERST, Republic of Djibouti (231 pp.). Chessex, R., Delaloye, M., Muller, J., Weidmann, M., 1975. Evolution of the volcanic region
Arnrsson, S., Andresdottir, A., 1995. Processes controlling the distribution of boron and of Ali-Sabieh (T.F.A.I) in the light of K/Ar age determinations. In: Pilger, A., Rsler, A.
chlorine in natural waters in Iceland. Geochim. Cosmochim. Acta 59:41254146. (Eds.), Afar Depression of Ethiopia 1. Schweiz., Stuttg., pp. 220227.
http://dx.doi.org/10.1016/0016-7037(95)00278-8. Clark, I.D., 2015. Groundwater Geochemistry and Isotopes. CRC Press, Taylor & Francis
Arnrsson, S., Gunnlaugsson, E., Svavarsson, H., 1983. The chemistry of geothermal Group, Boca Raton, Florida.
waters in Iceland III: chemical geothermometry in geothermal investigations. Correia, H., Fouillac, C., Gerard, A., Varet, J., 1985. The Asal geothermal eld (Republic of
Geochim. Cosmochim. Acta 47:567577. http://dx.doi.org/10.1016/0016- Djibouti). Geotherm. Resourc. Counc. Trans. 9, 513519.
7037(83)90278-8. Cortecci, G., Boschetti, T., Mussi, M., Herrera Lameli, C., Mucchino, C., Barbieri, M., 2005.
Asta, M.P., Gimeno, M.J., Auque, L.F., Gmez, J., Acero, P., Lapuente, P., 2012. New chemical and isotopic data on waters of El Tatio geothermal eld, Northern
Hydrochemistry and geothermometrical modeling of low-temperature Panticosa Chile. Geochem. J. 39:547571. http://dx.doi.org/10.2343/geochemj.39.547.
geothermal system (Spain). J. Volcanol. Geotherm. Res. 235236:8495. http://dx. Cowie, P.A., Scholz, C.H., 1992. Displacement-length scaling relationship for faults: data
doi.org/10.1016/j.jvolgeores.2012.05.007. synthesis and discussion. J. Struct. Geol. 14:11491156. http://dx.doi.org/10.1016/
Audin, L., Manighetti, I., Taponnier, P., Mtivier, F., Jacques, E., Huchon, P., 2001. Fault 0191-8141(92)90066-6.
propagation and climat control of sedimentation on the Ghoubbet Rift Floor: insights Craig, H., 1961. Isotopic variations in meteoric waters. Science 133:17021703. http://dx.
from the Tadjoura cruise in the western Gulf of Aden. Geophys. J. Int. 144:391413. doi.org/10.1126/science.133.3465.1702.
http://dx.doi.org/10.1046/j.0956-540x.2000.01322.x. Craig, H., Lupton, J.E., Horowiff, R.M., 1977. Isotope Geochemistry and Hydrology of Geo-
Awaleh, M.O., Hoch, F.B., Houssein, K.I., Soubaneh, Y.D., Egueh, N.M., Jalludin, M., thermal Waters in the Ethiopian rift valley. Scripps Institute of Oceanography, Uni-
Boschetti, T., 2015a. The geothermal resources of the Republic of Djibouti I: versity of California report, Technical report prepared for the United Nations
hydrogeochemistry of the Obock coastal hot springs. J. Geochem. Explor. 152: Development Program and the Ethiopian Government (http://escholarship.org/uc/
5466. http://dx.doi.org/10.1016/j.gexplo.2015.02.001. item/75k063gp 160 pp.).
Awaleh, M.O., Hoch, F.B., Boschetti, T., Soubaneh, Y.D., Egueh, N.M., Elmi, S.A., Jalludin, M., D'Amore, F., Giusti, D., Gizaw, B., 1997. Geochemical Assessment of the Northern
Khaireh, M.A., 2015b. The geothermal resources of the Republic of Djibouti II: geo- Tendaho Rift, Ethiopia. Proceedings, 22nd Workshop on Geothermal Reservoir Engi-
chemical study of the Lake Abhe geothermal eld. J. Geochem. Explor. 159:129147. neering, January 2729, SGP-TR-l55. Stanford University, Stanford, California,
http://dx.doi.org/10.1016/j.gexplo.2015.08.011. pp. 435446.
Awaleh, M.O., Baudron, P., Soubaneh, Y.D., Boschetti, T., Hoch, F.B., Egueh, N.M., Jalludi, M., D'Amore, F., Giusti, D., Abdallah, A., 1998. Geochemistry of the high-salinity geothermal
Dabar, O.A., Masse-Dufresne, J., Gassani, J., 2017. Recharge, groundwater ow pattern eld of Asal, Republic of Djibouti, Africa. Geothermics 27:197210. http://dx.doi.
and contamination processes in an arid volcanic area: insights from isotopic and geo- org/10.1016/S0375-6505(97)10009-8.
chemical tracers (Bara aquifer system, Republic of Djibouti). J. Geochem. Explor. 175: Daoud, M.A., Le Gall, B., Maury, R.C., Rolet, J., Huchon, P., Guillou, H., 2011. Young rift kine-
8298. http://dx.doi.org/10.1016/j.gexplo.2017.01.005. matics in the Tadjoura rift, western Gulf of Aden, Republic of Djibouti: Tadjoura rift
Ayenew, T., Kebede, S., Alemyahu, T., 2008. Environmental isotopes and hydrochemical kinematics. Tectonics 30:120. http://dx.doi.org/10.1029/2009TC002614.
study applied to surface water and groundwater interaction in the Awash River Darling, W.G., 2004. Helium and Carbon Isotopic Evidence for the Relationship between
basin. Hydrol. Process. 22:1548-1563. http://dx.doi.org/10.1002/hyp.6716. Outgassing and Structure in the East African Rift System. In: Wanty, R.B., Seal II,
Barberi, F., Ferrara, G., Santacroce, R., Varet, J., 1975. Structural Evolution of the Afar Triple R.R. (Eds.), WaterRock Interaction. Proceedings of the Eleventh International Sym-
Junction. In: Pilger, A., Rsler, A. (Eds.), Afar Depression of Ethiopia vol. 1. posium on WaterRock Interaction, Saratoga Springs, New York. Balkema Publ.,
Schweizerbart, Stuttgart, Germany, pp. 3854. London.
Barrat, J.A., Jahn, B.M., Fourcade, S., Joron, J.L., 1993. Magma genesis in an ongoing rifting Darling, W.G., Talbot, J.C., 1991. Evaluation and Development of Gas Geothermometry for
zone: the Tadjoura Gulf (Afar area). Geochim. Cosmochim. Acta 57:22912302. Geothermal Exploration in the East African Rift System. British Geological Survey,
http://dx.doi.org/10.1016/0016-7037(93)90570-M. Nottingham, UK (59 pp. (WD/91/072)).
Bayon, F.E.B., Ferrer, H., 2005. Sulphur Isotope Ratios in Philippine Geothermal Systems. Darling, W.G., Gizaw, B., Arusei, M.K., 1996. Lake-groundwater relationships and uid
Use of Isotope Techniques to Trace the Origin of Acidic Fluids in Geothermal Systems. rock interaction in the East African Rift Valley: isotopic evidence. J. Afr. Earth Sci.
IAEA-TECDOC-1448, pp. 111132. 22, 423431.
Bernard-Romero, R.A., Taran, Y.A., Pennisi, M., 2010. Geochemistry of Boron in Fluids of Davis, J.C., 1986. Statistics and Data Analysis in Geology. John Wiley & Sons, New York.
Los Humeros and Los Azufres Hydrothermal Systems, Mexico. In: Birkle, P., Torres Dekov, V.M., Egueh, N.M., Kamenov, G.D., Bayon, G., Lalonde, S.V., Schmidt, M., Liebetrau,
Alvarado, I.S. (Eds.), Proceedings of the 13th International Conference on Water- V., Munnik, F., Fouquet, Y., Tanimizu, M., Awaleh, M.O., Farah, I.G., Le Gall, B., 2014.
Rock Interaction, WRI-13, Guanajuato, Mexico, 1620 August 2010. CRC Press, Taylor Hydrothermal carbonate chimneys from a continental rift (Afar Rift): mineralogy,
& Francis Group, pp. 145148. geochemistry and mode of formation. Chem. Geol. 387:87100. http://dx.doi.org/
Bethke, C.M., Yeakel, S., 2008. The Geochemist's Workbench - Release 7. GWB Essentials 10.1016/j.chemgeo.2014.08.019.
Guide. Hydrogeology Program. University of Illinois, p. 489. Deniel, C., Vidal, P., Coulon, C., Vellutini, P.J., Piguet, P., 1994. Temporal evolution of mantle
BFGUR, 1999. Rsultats de la champagne des forages de reconnaissance effectue dans la sources during continental rifting: the volcanism of Djibouti (Afar). J. Geophys. Res.
Plaine de Hanl par BFGUR (Bundesanstalt fur Geowissenschaften und Rohstoffe). 99:2853-2869. http://dx.doi.org/10.1029/93JB02576.
Projet No 95.2050.3; BGR0119347. Hannover, Germany, October 1999. Assistance Doubre, C., Manighetti, I., Dorbath, C., Dorbath, L., Bertil, D., Delmond, J.C., 2007. Crustal
scientique au prs de lOfce National des Eaux de Djibouti (ONED), Republic of structure and magmato-tectonic processes in an active rift (AsalGhoubbet, Afar,
Djibouti (50 pp.). East Africa): insights from the 23-year recording of seismicity since the last rifting
BGR, 1982. Inventaire et mise en valeur des ressources en eau de la Rpublique de event. J. Geophys. Res. 112, B05406. http://dx.doi.org/10.1029/2006JB004333.
Djibouti. Coopration Hydrogologique Allemande. BGR (Bundesanstalt fr Drever, J.I., 1997. The Geochemistry of Natural water. Prentice Hall.
Geowissenschaften und Rohstoffe). Volume IV Inventaire des points deau. Projet Faure, G., 2001. Origin of Igneous Rocks: The Isotopic Evidence. Springer-Verlag, Berlin
N78.2233.1; BGR92705. Hannover, Germany, June 1982 (Republic of Djibouti. 157 Heidelberg GmbH.
pp.). Fontes, J.C., Pouchan, P., 1975. Les chemines du lac Abb (T.F.A.I.): stations
Blanc, P., Lassin, A., Piantone, P., Azaroual, M., Jacquemet, N., Fabbri, A., Gaucher, E.C., 2012. hydroclimatiques de l'Holocne. C. R. Acad. Sci. 280, 383386.
Thermoddem: a geochemical database focused on low temperature water/rock inter- Fontes, J.C., Florkowski, T., Pouchan, P., Zuppi, G.M., 1979. Preliminary Isotopic Study of
actions and waste materials. Appl. Geochem. 27:21072116. http://dx.doi.org/10. Lake Asal System (Republic of Djibouti). Application of Nuclear Techniques to the
1016/j.apgeochem.2012.06.002. Study of Lake Dynamics (ed Mortimer C), Vienna, Aug 20Sept 2, pp. 163174.
Fontes, J.C., Pouchon, P., Saliege, J.F., Zuppi, G.M., 1980. Environmental Isotope Study of Houssein, B., 2010. Geochemistry Overview of Hot Spring from the Lake Abhe Area: Re-
Groundwater Systems in the Republic of Djibouti. Arid-zone Hydrology: Investigations public of Djibouti. Proceedings Third East African Rift Geothermal Conference
with Isotope Techniques. IAEA, Vienna, pp. 237262. (ARGeo-C3), Djibouti. Republic of Djibouti, 2225 November 2010, pp. 158169.
Fontes, J.C., Sichre, M.C., Pouchan, P., Zuppi, G.M., 1989. Teneurs en brome et en chlore du Houssein, B., Chandrasekharam, D., Chandrasekharc, V., Jalludin, M., 2013. Geochemistry
lac Asal (Djibouti) et bilan en eau et en sels d'un systme vaporitique complexe. C. R. of thermal springs around Lake Abhe, Western Djibouti. Int. J. Sustainable Energy
Acad. Sci. 309, 701706. http://dx.doi.org/10.1080/14786451.2013.813027.
Fouillac, A.M., Fouillac, C., Cesbron, F., Pillard, F., Legendre, O., 1989. Water-rock Husson, F., Josse, J., L, S., Mazet, J., 2009. FactoMineR: Multivariate Exploratory Data Anal-
interaction between basalt and high-salinity uids in the Asal Rift, Republic ysis and Data Mining with R. R package version 1.12. (URL http://factominer.free.fr).
of Djibouti. Chem. Geol. 76:271289. http://dx.doi.org/10.1016/0009- Hutchison, W., Mather, T.A., Pyle, D.M., Biggs, J., Yirgu, G., 2015. Structural controls on
2541(89)90096-X. uid pathways in an active rift system: a case study of the Aluto volcanic complex.
Fournier, R.O., 1977. Chemical geothermometers and mixing model for geothermal sys- Geosphere 11:542562. http://dx.doi.org/10.1130/GES01119.1.
tems. Geothermics 5:4150. http://dx.doi.org/10.1016/0375-6505(77)90007-4. IAEA, 2007. Atlas of Isotope Hydrology Africa. International Atomic Energy Agency
Fournier, R.O., 1979. A revised equation for the Na/K geothermometer. Geotherm. (IAEA), UNESCO, Vienna.
Resourc. Counc. Trans. 3, 221224. IAH (International Association of Hydrogeologists), 1979. Map of mineral and thermal
Fournier, R.O., 1991. Water Geothermometers Applied to Geothermal Energy. In: water of Europe Scale 1:500,000 International Association of Hydrogeologists, UK.
D'Amore, F. (Ed.), Applications of Geochemistry in Geothermal Reservoir Develop- Jackson, J.A., White, N.J., Garfunkel, Z., Anderson, H., 1988. Relations between normal-fault
ment. UNITAR/UNDP publication, Rome, pp. 3769. geometry, tilting and vertical motions in extensional terrains: an example from the
Fournier, R.O., Potter II, R.W., 1979. Magnesium correction to NaKCa chemical southern Gulf of Suez. J. Struct. Geol. 10:155170. http://dx.doi.org/10.1016/0191-
geothermometer. Geochim. Cosmochim. Acta 43:15431550. http://dx.doi.org/10. 8141(88)90113-7.
1016/0016-7037(79)90147-9. JICA, 2014. Data Collection Survey on Geothermal Development in the Republic of
Fournier, R.O., Truesdell, A.H., 1973. An empirical NaKCa geothermometer for natural Djibouti. Final Report, December 2014. Japan International Cooperation Agency
waters. Geochim. Cosmochim. Acta 37:12551275. http://dx.doi.org/10.1016/0016- (JICA), The Republic of Djibouti.
7037(73)90060-4. JICA, 2015. The Project for Formulating Master Plan on Development of Geothermal Ener-
Franzson, H., Helgadttir, H.M., skarsson, F., 2015. Surface Exploration and First gy in Ethiopia. Final Report, April 2015. Japan International Cooperation Agency
Conceptual Model of the Dallol Geothermal Area, Northern Afar, Ethiopia. Proceed- (JICA), The Federal Democratic Republic of Ethiopia, Geological Survey of Ethiopia.
ings World Geothermal Congress 2015, Melbourne, Australia, 1925 April 2015 (11 Kaya, A., 2015. The effects of extensional structures on the heat transport mechanism: an
pp.). example from the Ortak geothermal eld (Byk Menderes Graben). J. Afr. Earth
Garca, M.G., Borgnino, L., 2015. Fluoride in the Context of the Environment. In: Preedy, Sci. 108:7488. http://dx.doi.org/10.1016/j.jafrearsci.2015.05.002.
V.R. (Ed.), Fluorine: Chemistry. Analysis, Function and Effects:pp. 321 http://dx. Kebede, S., 2013. Groundwater in Ethiopia - Features, Numbers and Opportunities.
doi.org/10.1039/9781782628507-00003 (Chapter 1). Springer-Verlag, Berlin Heidelberg.
Gasse, F., Fontes, J.C., 1989. Palaeoenvironments and palaeohydrology of a tropical closed Kebede, S., Travi, Y., Asrat, A., Alemayehu, T., Ayenew, T., Tessema, Z., 2008. Groundwater
lake (Lake Asal, Djibouti) since 10,000 yr B.P. Palaeogeogr. Palaeoclimatol. Palaeoecol. origin and ow along selected transects in Ethiopian rift volcanic aquifers. Hydrogeol.
69:67102. http://dx.doi.org/10.1016/0031-0182(89)90156-9. J. 16:5573. http://dx.doi.org/10.1007/s10040-007-0210-0.
Gasse, F., Dagain, J., Mazet, G., Richard, O., Fournier, M., 1987. Carte gologique de la Kehew, A.E., 2001. Applied Chemical Hydrogeology. Prentice Hall, Upper Saddle River,
Rpublique de Djibouti 1:100 000. Dikhil. Notice explicative. ISERST, Ministre New Jersey.
franais de la Coopration, Paris. Kerrich, R., 1986. Fluid inltration into fault zones: chemical, isotopic, and mechanical ef-
Gaulier, J.M., Huchon, P., 1991. Tectonic evolution of Afar triple junction. Bull. Soc. Geol. Fr. fects. Pure Appl. Geophys. 124:225268. http://dx.doi.org/10.1007/BF00875727.
162, 45464. Kusakabe, M., Komoda, Y., Takano, B., Abiko, T., 2000. Sulfur isotope effects in the dispro-
Geoffroy, L., Le Gall, B., Daoud, M.A., Jalludin, M., 2014. Flip-op detachment tectonics at portionation reaction of sulfur dioxide in hydrothermal uids: implications for the
nascent passive margins in SE Afar. J. Geol. Soc. 171:689694. http://dx.doi.org/10. 34S variations of dissolved bisulfate and elemental sulfur from active crater lakes.
1144/jgs2013-135. J. Volcanol. Geotherm. Res. 97:287308. http://dx.doi.org/10.1016/S0377-
Ghiglieri, G., Pittalis, D., Cerri, G., Oggiano, G., 2012. Hydrogeology and hydrogeochemistry 0273(99)00161-4.
of an alkaline volcanic area: the NE Mt. Meru slope (East African Rift Northern Kyser, T.K., O'Neil, J.R., 1984. Hydrogen isotope systematics of submarine basalts.
Tanzania). Hydrol. Earth Syst. Sci. 16:59541. http://dx.doi.org/10.5194/hess-16- Geochim. Cosmochim. Acta 48:21232133. http://dx.doi.org/10.1016/0016-
529-2012. 7037(84)90392-2.
Gianelli, G., Teklemariam, M., 1993. Water-rock interaction processes in the Aluto- Le Gall, B., Daoud, M.A., Maury, R.C., Rolet, J., Guillou, H., Sue, C., 2010. Magma-driven
Langano geothermal eld (Ethiopia). J. Volcanol. Geotherm. Res. 56:429445. antiform structures in the Afar rift: the Ali Sabieh range, Djibouti. J. Struct. Geol. 32:
http://dx.doi.org/10.1016/0377-0273(93)90007-E. 843854. http://dx.doi.org/10.1016/j.jsg.2010.06.007.
Giggenbach, W.F., 1988. Geothermal solute equilibria derivation of NaKMgCa Le Gall, B., Daoud, M.A., Rolet, J., Egueh, N.M., 2011. Large-scale exuring and antithetic
geoindicators. Geochim. Cosmochim. Acta 52:27492765. http://dx.doi.org/10.1016/ extensional faulting along a nascent plate boundary in the SE Afar rift: structure of
0016-7037(88)90143-3. a nascent plate boundary in SE Afar. Terra Nova 23:416420. http://dx.doi.org/10.
Giggenbach, W.F., 1991a. Chemical Techniques in Geothermal Exploration. In: D'Amore, F. 1111/j.1365-3121.2011.01029.x.
(Ed.), Applications of Geochemistry in Geothermal Reservoir Development. UNITAR/ Manighetti, I., Tapponnier, P., Gillot, P.Y., Jacques, E., Courtillot, V., Armijo, R., Ruegg, J.C.,
UNDP publication, Rome, pp. 119142. King, G., 1998. Propagation of rifting along the Arabia-Somalia plate boundary: into
Giggenbach, W.F., 1991b. Isotopic Composition of Geothermal Waters and Steam Dis- Afar. J. Geophys. Res. 103:49474974. http://dx.doi.org/10.1029/97JB02758.
charges. In: D'Amore, F. (Ed.), Applications of Geochemistry in Geothermal Reservoir Marques, J.M., Espinha, M.J., Carreira, P.M., Graa, R.C., Aires-Barros, L., Carvalho, J.M.,
Development. UNITAR/UNDP publication, Rome, pp. 253273. Chamin, H.I., Borges, F.S., 2003. Geothermal uids circulation at Caldas do Moledo
Giggenbach, W.F., 1995. Geochemical Exploration of a Difcult Geothermal System, area, Northern Portugal: geochemical and isotopic signatures. Geouids 3:189201.
Paraso, Vella Lavella, Solomon Islands. Proceedings of the World Geothermal Con- http://dx.doi.org/10.1046/j.1468-8123.2003.00059.x.
gress, Florence, Italy, pp. 9951000. Meng, S.X., Maynard, J.B., 2001. Use of statistical analysis to formulate conceptual models
Gizaw, B., 1996. The origin of high bicarbonate and uoride concentrations in waters of of geochemical behavior: water chemical data from the Botucatu aquifer in Sao Paulo
the Main Ethiopian Rift Valley, East African Rift system. J. Afr. Earth Sci. 22: state, Brazil. J. Hydrol. 250:7897. http://dx.doi.org/10.1016/S0022-1694(01)00423-1.
391402. http://dx.doi.org/10.1016/0899-5362(96)00029-2. Michard, G., Beaucaire, C., 1993. Les eaux thermals des granites de Galicie (Espagne): des
Goldstein, S.J., Jacobsen, S.B., 1987. The Nd and Sr isotopic systematics of river-water dis- eaux carbogazeuses aux eaux alcalines (thermal waters from granites of Galicia
solved material - implications for the sources of Nd and Sr in seawater. Chem. Geol. (Spain): from CO2-rich to high pH waters). Chem. Geol. 110:345360. http://dx.
66:245272. http://dx.doi.org/10.1016/0168-9622(87)90045-5. doi.org/10.1016/0009-2541(93)90328-G.
Gonantini, R., Borsi, S., Ferrara, G., Panichi, C., 1973. Isotopic composition of waters from Mlynarski, M., Zlotnicki, J., 2001. Fluid circulation in the active emerged Asal rift (east
Danakil depression (Ethiopia). Earth Planet. Sci. Lett. 18:1321. http://dx.doi.org/10. Africa, Djibouti) inferred from self-Potential and Telluric Telluric Prospecting.
1016/0012-821X(73)90028-9. Tectonophysics 339:455472. http://dx.doi.org/10.1016/S0040-1951(01)00127-5.
Gler, C., Thyne, G.D., 2004. Hydrologic and geologic factors controlling surface Mller, P., Rosenthal, E., Inbar, N., Magri, F., 2016. Hydrochemical considerations for iden-
and groundwater chemistry in Indian Wells-Owens Valley area, southeastern tifying water from basaltic aquifers: the Israeli experience. J. Hydrol. 5:3347. http://
California, USA. J. Hydrol. 285:177198. http://dx.doi.org/10.1016/j.jhydrol.2003.08. dx.doi.org/10.1016/j.ejrh.2015.11.016.
019. Moussa, N., Rouxel, O., Grassineau, N.V., Ponzevera, E., Nonnotte, P., Fouquet, Y., Le Gall, B.,
Gler, C., Thyne, G.D., McCray, J.E., Turner, A.K., 2002. Evaluation of graphical and multi- 2016. Sulfur and strontium isotopic study of epithermal mineralization: a case study
variate statistical methods for classication of water chemistry data. Hydrogeol. J. from the SE Afar Rift, Djibouti. Ore Geol. Rev. http://dx.doi.org/10.1016/j.oregeorev.
10:455474. http://dx.doi.org/10.1007/s10040-002-0196-6. 2016.10.028 (in press).
Gunnarsson, I., Arnrsson, S., 2000. Amorphous silica solubility and the thermodynamic Nicholson, K.N., 1993. Geothermal Fluids: Chemistry and Exploration Techniques. Spring-
properties of H4SiO4 in the range of 0 to 350 C at Psat. Geochim. Cosmochim. Acta er-Verlag, Berlin.
64:22952307. http://dx.doi.org/10.1016/S0016-7037(99)00426-3. Noir, J., Jacques, E., Bekri, S., Adler, P.M., Tapponnier, P., King, G.C.P., 1997. Fluid ow trig-
Gupta, A.K., Ayoob, S., 2016. Fluoride in Drinking Water: Status, Issues and Solutions. CRC gered migration of events in the 1989 Dobi earthquake sequence of Central Afar.
Press, Taylor & Francis Group, Boca Raton, Florida. Geophys. Res. Lett. 24, 23352338.
Hemming, N.G., Reeder, R.J., Hanson, G.N., 1995. Mineral-uid partitioning and isotopic Norton, D., Knapp, R., 1977. Transport phenomena in hydrothermal systems; the nature of
fractionation of boron in synthetic calcium carbonate. Geochim. Cosmochim. Acta porosity. Am. J. Sci. 277:913936. http://dx.doi.org/10.2475/ajs.277.8.913.
59:371379. http://dx.doi.org/10.1016/0016-7037(95)00288-B. Ohmoto, H., Lasaga, A.C., 1982. Kinetics of reactions between aqueous sulfates and sul-
Hoefs, J., 2015. Stable Isotope Geochemistry. seventh ed. Springer International Publish- des in hydrothermal systems. Geochim. Cosmochim. Acta 46:17271745. http://
ing, Switzerland. dx.doi.org/10.1016/0016-7037(82)90113-2.
Oppenheimer, C., Fischer, T.P., Scaillet, B., 2014. Volcanic Degassing: Process and Impact. Teklemariam, M., Beyene, K., 2001. Geochemical Monitoring of the Aluto-Langano Geo-
In: Holland, H.D., Turekian, K.K. (Eds.), Treatise on Geochemistry 2nd Edition Vol- thermal Field. Proceedings, Twenty-Sixth Workshop on Geothermal Reservoir Engi-
ume 4: The Crust:pp. 111179 http://dx.doi.org/10.1016/B978-0-08-095975-7. neering Stanford University, Stanford, California, January 2931, 2001, SGP-TR-168.
00304-1. Tesfaye, S., Rowan, M.G., Mueller, K., Trudgill, B.D., Harding, D.J., 2008. Relay and accom-
Pang, Z.H., Armannsson, H., 2006. Analytical Procedures and Quality Assurance for Geo- modation zones in the Dobe and Hanle grabens, central Afar, Ethiopia and Djibouti.
thermal Water Chemistry. United Nations University, Geothermal Training Pro- J. Geol. Soc. 165:535547. http://dx.doi.org/10.1144/0016-76492007-093.
gramme (Reykjavk, Iceland). UNDP (United National Development Program), 1973. Geology, Geochemistry and Hy-
Panichi, C., 1995. Isotopic Investigation in Geothermal Hydrology. International Atomic drology of the East Africa Rift System within Ethiopia. Technical report prepared for
Energy Agency, Report of an Expert Mission (Project number ETH/8/003). the Imperial Ethiopian Government for the United Nations Development Programme,
Parkhurst, D.L., Appelo, C.A.J., 2013. Description of Input and Examples for PHREEQC Ver- United Nations, New York (227 pp.).
sion 3 - A Computer Program for Speciation, Batch-Reaction, One-Dimensional Trans- Varet, J., 1975. Geological Map of Central and Southern Afar (Ethiopia and Djibouti
port, and Inverse Geochemical Calculations. U.S. Geological Survey Techniques and Republic).
Methods, book 6, chap. A43 (497 p., available only at http://pubs.usgs.gov/tm/06/ Vellutini, P., 1990. The Manda-lnakir Rift, Republic of Djibouti: a comparison with the
a43/). Asal. Rift and its geodynamic interpretation. Tectonophysics 172 (1990):141153.
Parkhurst, D.L., Charlton, S.R., 2008. NetpathXL An Excel Interface to the program http://dx.doi.org/10.1016/0040-1951(90)90065-G.
NETPATH. U.S. Geological Survey Techniques and Methods 6-A26, Reston, Virginia. Vengosh, A., 2014. Salinization and Saline Environments. In: Holland, H.D., Turekian, K.K.
Pierret, M.C., Clauer, N., Bosch, D., Blanc, G., France-Lanord, C., 2001. Chemical and isotopic (Eds.), Treatise on Geochemistry, second ed. vol. 11. Environmental Geochemistry:
(87Sr/86Sr, 18O, D) constraints to the formation processes of Red-Sea brines. pp. 325378. http://dx.doi.org/10.1016/B978-0-08-095975-7.00909-8.
Geochim. Cosmochim. Acta 65:12591275. http://dx.doi.org/10.1016/S0016- Vengosh, A., Heumann, K.G., Juraske, S., Kasher, R., 1994. Boron isotope application for
7037(00)00618-9. tracing sources of contamination in groundwater. Environ. Sci. Technol. 28:
R Core Team, 2016. R: A Language and Environment for Statistical Computing. R Founda- 19681974. http://dx.doi.org/10.1021/es00060a030.
tion for Statistical Computing, Vienna, Austria (URL https://www.R-project.org/). Vengosh, A., Kolodny, Y., Spivack, A.J., 1998. Ground-water Pollution Determined by
Rango, T., Vengosh, A., Dwyer, G., Bianchini, G., 2013. Mobilization of arsenic and other Boron Isotope Systematic. IAEA. Application of Isotope Techniques to Investigate
naturally occurring contaminants in groundwater of the Main Ethiopian Rift aquifers. Groundwater Pollution. IAEA-TECDOC-1046, pp. 1738.
Water Res. 47:58015818. http://dx.doi.org/10.1016/j.watres.2013.07.002. Vengosh, A., Spivack, A.J., Yohanan, A., Ayalon, A., 1999. Geochemical and boron, stron-
Reyes, A.G., Vickridge, I.C., 1996. Distribution of Lithium, Boron and Chloride between tium, and oxygen isotopic constraints on the origin of the salinity in groundwater
Fresh and Altered Rocks in the Kawerau Geothermal System, New Zealand. Proceed- from the Mediterranean coast of Israel. Water Resour. Res. 35, 18771894.
ings 18th Geothermal Workshop 1996. University of Auckland. Verhagen, B.T., Geyh, M.A., Frhlich, K., Wirth, K., 1991. Isotope Hydrological Methods for
Robinson, R., 1973. Sulfur isotopic equilibrium during sulfur hydrolysis at high tempera- the Quantitative Evaluation of Ground Water Resources in Arid and Semi-arid Areas.
ture. Earth Planet. Sci. Lett. 18, 443450. Development of a Methodology. Federal Ministry for Economic Cooperation, Bonn.
Rye, R.O., Bethke, P.M., Wasserman, M.D., 1992. The stable isotope geochemistry of acid Verma, M.P., 2001. Silica Solubility Geothermometers for Hydrothermal Systems. Pro-
sulfate alteration. Econ. Geol. 87:225262. http://dx.doi.org/10.2113/gsecongeo.87. ceedings of the Tenth International Symposium on Water-Rock Interaction, WRI-10
2.225. (ed Cidu R), Vol 1, 34952, Villasimius, Italy, June 1015.
Sakai, H., 1968. Isotopic properties of sulphur compounds in hydrothermal processes. Verma, M.P., Santoyo, E., 1997. New improved equations for Na/K, Na/Li and SiO2
Geochem. J. 2:2949. http://dx.doi.org/10.2343/geochemj.2.29. geothermometers by outlier detection and rejection. J. Volcanol. Geotherm. Res. 79:
Sanjuan, B., Michard, G., Michard, A., 1990. Origine des substances dissoutes dans les eaux 924. http://dx.doi.org/10.1016/S0377-0273(97)00024-3.
des sources thermales et des forages de la rgion Asal-Goubhet (Rpublique de Vidal, P., Deniel, C., Vellutini, P.J., Piguet, P., Coulon, C., Vincent, J., Audin, J., 1991. Changes
Djibouti). J. Volcanol. Geotherm. Res. 43:333352. http://dx.doi.org/10.1016/0377- of mantle source in the course of a rift evolution: the Afar case. Geophys. Res. Lett. 18:
0273(90)90060-S. 19131916. http://dx.doi.org/10.1029/91GL02006.
Sanjuan, B., Romain, M., Asmundsson, R., Michel, B., Giroud, N., 2014. Use of two new Na/ Virkir-Orkint, 1990. Djibouti. Geothermal Scaling and Corrosion Study. Virkir-Orkint,
Li geothermometric relationships for geothermal uids in volcanic environments. Reykjavk, report (109 pp.).
Chem. Geol. 389:6081. http://dx.doi.org/10.1016/j.chemgeo.2014.09.011. Wallace, P.J., Edmonds, M., 2011. The sulfur budget in magmas: evidence from melt inclu-
Schoell, M., Faber, E., 1976. E. Survey on the isotopic composition of waters from NE sions, submarine glasses, and volcanic gas emissions. Rev. Mineral. Geochem. 73:
Africa. Geol. Jahrb. D 17, 197213. 215246. http://dx.doi.org/10.2138/rmg.2011.73.8.
Shanks III, W.C., Bischoff, J.L., Rosenbauer, R.J., 1981. Seawater sulfate reduction and sulfur Ward Jr., J.H., 1963. Hierarchical grouping to optimize an objective function. J. Am. Stat.
isotope fractionation in basaltic systems: interaction of seawater with fayalite and Assoc. 58:236244. http://dx.doi.org/10.1080/01621459.1963.10500845.
magnetite at 200350 C. Geochim. Cosmochim. Acta 45:19771995. http://dx.doi. WHO (World Health Organization), 2011. Guidelines for Drinking-water Quality. fourth
org/10.1016/0016-7037(81)90054-5. ed. (Geneva, Switzerland. http://apps.who.int/iris/bitstream/10665/44584/1/
Shikazono, N., 2003. Geochemical and Tectonic Evolution of Arc-Backarc Hydrothermal 9789241548151_eng.pdf).
Systems - Implication for the Origin of Kuroko and Epithermal Vein-Type mineraliza- Williams, F.M., 2016. Understanding Ethiopia Geology and Scenery. Springer Interna-
tions and the Global Geochemical Cycle. Developments in Geochemistry 8. The tional Publishing, Switzerland.
Netherlands, Elsevier (463 pp.). Yitbarek, A., Razack, M., Ayenew, T., Zemedagegnehu, E., Azagegn, T., 2012.
Swanson, S., Bahr, J.M., Schwar, M.T., Potter, K.W., 2001. Two-way cluster analysis of geo- Hydrogeological and hydrochemical framework of Upper Awash River basin,
chemical data to constrain spring source waters. Chem. Geol. 179:7391. http://dx. Ethiopia: with special emphasis on inter-basins groundwater transfer between Blue
doi.org/10.1016/S0009-2541(01)00316-3. Nile and Awash Rivers. J. Afr. Earth Sci. 65, 4660.
Tapponnier, P., Armijo, R., Manighetti, I., Courtillot, V., 1990. Bookshelf faulting and hori- YuanYuan, L., MianPing, Z., Ping, Z., RongHua, X., 2014. Geochemical processes and origin
zontal block rotations between overlapping rifts in southern Afar. Geophys. Res. Lett. of boron isotopes in geothermal water in the Yunnan-Tibet geothermal zone. Sci.
17:14. http://dx.doi.org/10.1029/GL017i001p00001. China Earth Sci. 12:29342944. http://dx.doi.org/10.1007/s11430-014-4940-2.
Taran, T., Zelenski, M., 2015. Systematics of Water Isotopic Composition and Chlorine Zumbo, V., Fraud, G., Vellutini, P., Piguet, P., Vincent, J., 1995. First 40Ar/ 39Ar dating on
Content in Arc-volcanic Gases. In: Zellmer, G.F., Edmonds, M., Straub, S.M. (Eds.), Early Pliocene to Plio-Pleistocene magmatic events of the Afar - Republic of
The Role of Volatiles in the Genesis, Evolution and Eruption of Arc Magmas. Geolog- Djibouti. J. Volcanol. Geotherm. Res. 65:281295. http://dx.doi.org/10.1016/0377-
ical Society, London, Special Publications:p. 410 http://dx.doi.org/10.1144/SP410.5. 0273(94)00107-R.
Tarcan, G., 2005. Mineral saturation and scaling tendencies of waters discharged from
wells (N150 C) in geothermal areas of Turkey. J. Volcanol. Geotherm. Res. 142:
263283. http://dx.doi.org/10.1016/j.jvolgeores.2004.11.007.
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Geochemical study of the Sakalol Harralol

Article in Journal of Volcanology and Geothermal Research November 2016

Mohamed Osman Awaleh Tiziano Boschetti

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Moussa mahdi ahmed Nima Moussa

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Wastewater reuse : Innovative technologies for saline wastewater View project

Contents lists available at ScienceDirect

Journal of Volcanology and Geothermal Research

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

Geochemical study of the Sakalol-Harralol geothermal eld (Republic of

1. Introduction the Republic of Djibouti for estimating their geothermal potential

Parameter Unit Cluster 1 Cluster 2 Cluster 3 *Cluster 4

NaClHCO3-SO4 NaCl NaCl NaCl

Mean St.dev. Mean St.dev. Mean St.dev. Mean St.dev.

EC (S/cm) 1928 654 6607 1509 9778 1294 22660 -

N: number of sampled springs (2015).

Cluster # Sample Sample name 18O(H2O) 2H(H2O) 13C(DIC) *13C(CO2) 14

1 1 douffalou 1 3.90 28.1 - - - 12.8 8.16 11.49 0.7057

Abhe T.A.D.D. geothermal well

#35 Na-HCO3 waters 45

Cluster 1 geothermal well geothermal well

Sakalol Cluster 2 Asal hot spring Hanl borehole seawater

Cluster 3 Lake Asal hot-warm-cold springs

Verhagen et al. 1991

-20 mean s.d.

Erta Ale geothermal well

-22 deep geothermal well

-34 Abhe springs

Schoell & Faber 1976 Agna

well-borehole BFGUR 1999

seawater Lake Asal

0.8 #35 Acid Tuff

borehole geothermal well

Dobi water with Cl > 1 g/l

with respect to amorphous silica (SI = 0.29 0.09; see supporting

mean local air

or thermo.com.v8.r6+.dat database 4.5. Dissolved sulfate: origin traced by isotope

this study literature

Cluster 4 Dobi Cl > 1 g/l waters

S(SO4 ) ( vs. V-CDT)

this work literature

the geothermal waters in that area (e.g. 71 17 mg/l in the Aluto-

this study literature

Asal geothermal reservoir

this study literature

agriculture drainage #74

this study literature

water-silicate interaction -12

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