R E P O RT
Environmental isotopes (18O, 2H, and 87Sr/86Sr)
as a tool in groundwater investigations in the Keta Basin, Ghana
Niels O. Jørgensen · Bruce K. Banoeng-Yakubo
Abstract Analyses of environmental isotopes (18O, 2H,
and 87Sr/86Sr) are applied to groundwater studies with
emphasis on saline groundwater in aquifers in the Keta
Basin, Ghana. The 87Sr/86Sr ratios of groundwater and
surface water of the Keta Basin primarily reflect the ge-
ology and the mineralogical composition of the forma-
tions in the catchments and recharge areas. The isotopic
compositions of 18O and 2H of deep groundwater have
small variations and plot close to the global meteoric wa-
ter line. Shallow groundwater and surface water have
considerably larger variations in isotopic compositions,
which reflect evaporation and preservation of seasonal
fluctuations. A significant excess of chloride in shallow
groundwater in comparison to the calculated evaporation
loss is the result of a combination of evaporation and
marine sources. Groundwaters from deep wells and dug
wells in near-coastal aquifers are characterized by rela-
tively high chloride contents, and the significance of ma-
rine influence is evidenced by well-defined mixing lines
for strontium isotopes, and hydrogen and oxygen stable
isotopes, with isotopic compositions of seawater as one
end member. The results derived from environmental
isotopes in this study demonstrate that a multi-isotope
approach is a useful tool to identify the origin and sourc-
es of saline groundwater.
Résumé L’analyse des isotopes du milieu (18O, 2H, et
87Sr/86Sr)a été mise en œuvre pour des études hydrogéo-
logiques portant sur des eaux souterraines salées des
aquifères du bassin de Keta (Ghana). Les rapports isoto-
piques 87Sr/86Sr de l’eau souterraine et de l’eau de surfa-
ce du bassin de Keta reflètent principalement la géologie
Received: 16 March 2000 / Accepted: 29 November 2000
Published online: 9 March 2001
© Springer-Verlag 2001
N.O. Jørgensen (✉)
Geological Institute, University of Copenhagen,
Øster Voldgade 10, DK-1350 Copenhagen, Denmark
e-mail: nielsoj@geo.geol.ku.dk
Fax: +45-33-148322
B.K. Banoeng-Yakubo
Department of Geology, University of Ghana,
P.O. Box 58, Legon, Ghana
Hydrogeology Journal (2001) 9:190–201
et la composition minéralogique des formations des bas-
sins d’alimentation et des zones de recharge. Les compo-
sitions isotopiques en 18O et en 2H des eaux souterraines
profondes présentent de faibles variations et se placent
près de la droite des eaux météoriques mondiales. Les
eaux des nappes peu profondes et les eaux de surface su-
bissent des variations beaucoup plus fortes de leurs com-
positions isotopiques, dues à l’évaporation et aux fluc-
tuations saisonnières. Un excès significatif en chlorures
dans les eaux souterraines peu profondes, compte tenu
de l’évaporation calculée, résulte à la fois de l’évapora-
tion et d’apports marins. Les eaux souterraines de fora-
ges profonds et de puits dans les aquifères proches de la
côte sont caractérisées par des concentrations relative-
ment élevées en chlorure; une influence marine signifi-
cative est mise en évidence par des droites de mélange
bien définies pour les isotopes du strontium et les isoto-
pes stables de l’oxygène et de l’hydrogène, avec les
compositions de l’eau de mer pour l’un des termes du
mélange. Les résultats fournis par les isotopes du milieu
dans cette étude montrent qu’une approche multi-isotopi-
que est un outil pertinent pour identifier l’origine et les
sources d’eaux souterraines salées.
Resumen Se ha aplicado el análisis de los isótopos am-
bientales (18O, 2H y 87Sr/86Sr) al estudio de las aguas
subterráneas en la Cuenca de Keta (Ghana), haciendo én-
fasis en acuíferos salinizados. Las proporciones de
87Sr/86Sr en las aguas subterráneas y superficiales de la
Cuenca de Keta reflejan, fundamentalmente, la geología
y la composición mineralógica de las formaciones domi-
nantes en las zonas de captación y de recarga. La compo-
sición isotópica de las aguas subterráneas profundas pre-
senta variaciones pequeñas en 18O y 2H y se acerca a la
línea meteórica mundial. Las aguas subterráneas someras
y las superficiales presentan variaciones considerable-
mente mayores en la composición isotópica, hecho que
refleja la evaporación y las fluctuaciones estacionales.
Como resultado de la combinación entre evaporación e
influencia marina, se observa un exceso significativo de
cloruros en las aguas subterráneas someras en compara-
ción con las pérdidas por evaporación. Las aguas subte-
rráneas de pozos profundos y de pozos excavados en
acuíferos cercanos a la costa se caracterizan por sus con-
tenidos relativamente altos de cloruros. La influencia
marina se evidencia por las líneas de mezcla bien defini-
DOI 10.1007/s100400000122

das por los isótopos del estroncio y los isótopos estables
del hidrógeno y oxígeno, mientras que la composición
isotópica del agua marina se comporta como punto extre-
mo de dichas líneas. Los resultados obtenidos en este
trabajo a partir de los isótopos ambientales demuestran
que el enfoque multi-isotópico es una herramienta útil
para identificar el origen y las fuentes de aguas subterrá-
neas salinas.
Keywords stable isotopes · radioactive isotopes ·
salinization · salt-water/fresh-water relations · Ghana
Introduction
The Keta Basin is one of several fault-controlled sedi-
mentary basins in West Africa along the southeastern
coast of Ghana and dominated by the Volta River estu-
ary. The sedimentary sequence in the Keta Basin consti-
tutes one of the most prolific aquifer systems in Ghana
(Nerquaye-Tetteh 1993; Bannerman 1994; Frempong
and Kortatsi 1994; Dapaah-Siakwan and Gyau-Boakye
2000). Therefore, groundwater plays a vital role in the
domestic water supply and in farming economies and,
furthermore, supplies the fairly large communities living
along the coastal strip between the outlet of the Volta
River and the Ghanaian-Togo border. Locations are
shown in Fig. 1.
Many dug wells (<10 m deep) in Quaternary to Neo-
gene clastic sediments are used for domestic water sup-
ply, watering of livestock, and for dry-season irrigation
purposes. Furthermore, extensive drilling activities in the
1950s confirmed the existence of deeper aquifers in Cre-
taceous-Eocene limestones, which have since been ex-
ploited for urban water supply. Hydrochemical analyses
of this deep groundwater indicate that the groundwater
quality in the Keta Basin is generally considered to be
usable for drinking water and agricultural purposes.
However, a major problem in drinking-water quality
and management of domestic water supply in the Keta
Basin is salinization of groundwater in dug wells and in
deep boreholes (Gill 1969; Bannerman 1994). Many
prospected well sites have not been completed due to sa-
linity problems in the aquifers, and existing deep wells
and dug wells have been abandoned due to increasing sa-
linity over time. In the absence of surface-water sources
in close proximity of the communities, several attempts
have been made to find sufficient groundwater resources
on which to base the public water supply. Infiltration of
seawater into the groundwater has been observed in
some deep boreholes drilled along the coastal strip and
saline groundwater exists in aquifers at shallow depths a
few kilometres inland.
Three major sources of chloride contamination are to
be considered in this area: (1) seawater and brackish-
water intrusion from the nearby Gulf of Guinea and the
Keta Lagoon (Fig. 1b); (2) dissolved Cl originating from
sea-spray and marine aerosols deposited in the topsoil;
and (3) evaporative enrichment. The objective of this
Hydrogeology Journal (2001) 9:190–201
191
study is to analyse four major aquifers in the Keta Basin
by means of environmental isotopes (18O, 2H, and
87Sr/86Sr) in order to identify the source of salinization of
deep and shallow groundwater.
Geologic and Hydrogeologic Setting
The Keta Basin is a fault-controlled Mesozoic/Tertiary
sedimentary basin along the coast of the Gulf of Guinea.
The basement complex consists of early Precambrian
Dahomeyan gneisses, migmatites, and schists. These
rocks were affected by the Pan-African orogeny and crop
out along fringes of the basin to the north (Fig. 1b). The
basal sedimentary sequence in the basin is known from
borehole data and comprises Lower to Middle Devonian
marine shale, sandstone, and siltstone, which are over-
lain by Jurassic dolerites and sills (Akpati 1978). A se-
ries of Cretaceous-Eocene marine sediments, composed
of limestone, shale, and glauconitic sandstone, crops out
on the eastern edge of the basin close to the Togo–Ghana
boundary. The sandstones and limestones are highly con-
solidated and dip and thicken toward the coast in the
southwest. In the northeastern part of the basin occur
scattered surficial deposits of Neogene continental sedi-
ments that unconformably overlie the Cretaceous-Eoc-
ene limestones and sandstones; these sediments are
mainly made up of unconsolidated to semi-consolidated
limonitic argillaceous sands with gravelly beds at the
base. The central part of the basin, occupied by the Keta
Lagoon, is dominated by Quaternary unconsolidated
coastal sediments, marine sands, and gravels, which are
on average 30 m thick around Keta, though they thicken
toward the Volta River estuary.
Four major aquifers in the Keta Basin are distin-
guished according to the geography and the geological
setting (Nerquaye-Tetteh 1993):
1. Weathered Dahomeyan gneisses along the northeast-
ern rim of the basin. They crop out around Akatsi and
are locally overlain by Neogene to Recent continental
sedimentary deposits of sands and gravels. Ground-
water occurs in both the weathered gneisses and surfi-
cial sediments.
2. Surficial Neogene continental deposits of unconsoli-
dated to semi-consolidated limonitic argillaceous
sands in the northeastern and central parts of the ba-
sin.
3. Cretaceous-Eocene marine limestones and sandstone
beds that are exploited for drinking water in the cen-
tral and southeastern parts of the basin; these units
constitute the major and most important deeper aqui-
fer in the Keta Basin.
4. Quaternary coastal marine sands and gravels in the
Volta River estuary and Keta Lagoon area. These
surficial deposits of unconsolidated sand and gravel
are generally associated with high groundwater re-
charge. However, areas below sea level may periodi-
cally undergo salinization due to seawater intrusion
(Gill 1969; Nerquaye-Tetteh 1993).
DOI 10.1007/s100400000122
192

The Keta Basin is located in the dry equatorial zone

dominated by tropical maritime air masses (monsoon)
from the South Atlantic Ocean. Mean annual rainfall is
810–870 mm (Akiti 1987; Dickson and Benneh 1995).
The rainfall is seasonal with two rainy and two dry sea-
sons. More than 70% of the rainfall occurs in the major
wet season, during April–July. The secondary rainy sea-
son is during September–November. The average month-
ly relative humidity is 65–75% and the annual mean
temperature is 27.2 °C in Big Ada and 27.0 °C in
Sogakofe (Fig. 1b).

Sampling and Analytical Techniques

Water sampling took place during two periods, firstly in
the rainy season, October 1996, and secondly toward the
end of the dry season, in February–March 1998. Ground-
water samples were collected twice from 15 boreholes
and 18 dug wells. All deep wells and dug wells listed are
used for drinking-water supply except for wells B15
Denu and B22 Anloga, which yield saline groundwater.
Surface water was collected at six sites from the Volta
River close to the delta outlet and from the Keta Lagoon.

Fig. 1 a Location of the Keta Basin, Ghana. b Geological map of

the Keta Basin, showing locations of deep wells, dug wells, and
surface-water sampling sites

Hydrogeology Journal (2001) 9:190–201 DOI 10.1007/s100400000122


Seawater samples were collected in the Gulf of Guinea
west of Ada Foah and off Keta (Fig. 1b). On-site analys-
es comprised temperature and electrical conductivity
(EC) corrected to 25 °C. Boreholes and dug wells were
pumped until stable readings for these parameters were
obtained. Samples were collected in acid-washed poly-
ethylene bottles and filtered (0.45 µm) for subsequent
laboratory analysis. Locations of sampled wells and sur-
face-water sites are shown in Fig. 1b.
The Cl contents in water samples were determined by
a digital titrator using the mercury nitrate method. The
Sr analyses were carried out with a Perkin-Elmer Atomic
Absorption Spectrophotometer model 460. The oxygen
stable-isotope analyses of water samples were obtained
on a VG Sira 10 mass spectrometer with automatic inlet.
The water samples for stable hydrogen isotope analyses
were reduced to H2 by use of zinc in quartz ampoules at
700 °C (Coleman et al. 1982). The analyses were carried
out in a Finnigan MAT 250 triple collector mass spec-
trometer. The results for both isotopes are expressed in
per mill (‰) deviation from the VSMOW standard using
the δ-scale. Reproducibility is better than 0.1‰ for δ18O
and about 1‰ for δ2H.
Freeze-dried 50-mL water samples were analysed for
87Sr/86Sr ratios. The dry matter was dissolved in 6 N HCl
and evaporated to dryness. Subsequently, Sr was separat-
ed from a 2.5 N HCl solution by conventional ion ex-
change. Approximately 1 µg SrCl2 was mounted on tan-
talum filaments with phosphoric acid. The Sr isotopic
composition was measured on an 8-collector Fisons Sec-
tor 54–30 mass spectrometer. Data were collected by
multidynamic analysis, and exponential mass-fraction-
ation was assumed in the applied correction to a 86Sr/88Sr
ratio of 0.1194. Within-run precision was typically
±0.000005 (1 s.d.) on 87Sr/86Sr and always better than
±0.000007. In the course of data acquisition, average and
reproducibility of measured values of the international
standard material NBS987 were 87Sr/86Sr=0.710245±
0.000011 (1 s.d.), n=37.
The oxygen-isotope analyses were determined at the
Geophysical Institute, Copenhagen University. Determi-
nations of the Sr and Cl contents and strontium- and hy-
drogen-isotope analyses were made in laboratory facili-
ties at the Geological Institute and the Danish Centre for
Isotope Geology at the University of Copenhagen.
Results
Electrical Conductivity and Strontium
and Chloride Contents
Results of EC measurements are shown in Table 1. The
EC is generally less than 1,500 µS/cm for both shallow
and deep groundwaters. Several deep wells in the weath-
ered gneisses and dug wells in continental Neogene sedi-
ments yield groundwater with EC of 1,000–2,300 µS/cm,
and groundwater samples obtained from two of the in-
vestigated deep wells (B15 Denu and B22 Anloga) in the
Cretaceous-Eocene limestone aquifer show an enhanced
Hydrogeology Journal (2001) 9:190–201
193
Fig. 2 Relation between log chloride and log strontium for shal-
low (1,2) and deep (3–5) groundwaters in the Keta Basin. The
Cl–Sr seawater line is shown for reference
EC of approximately 5,000 and 12,000 µS/cm, respec-
tively.
The chloride and strontium contents of groundwater
samples are shown in Table 1 and in Fig. 2. The relation-
ship between Sr and Cl in seawater is shown for refer-
ence. The Sr contents are generally low, 0.5–1.5 mg/L
Sr, and the Cl contents are generally 50–475 mg/L. How-
ever, groundwater samples from two deep boreholes
in the Eocene-Cretaceous limestone aquifer (B15 Denu
and B22 Anloga) have high Cl contents, 1,525 and
3,475 mg/L, respectively.
A positive correlation exists between contents of Sr
and Cl within groundwaters from the individual aquifers
studied (Fig. 2). Only two deep boreholes in the Creta-
ceous-Eocene limestone aquifer, B15 Denu and B22 An-
loga, yielded high-Cl groundwaters that deviate signifi-
cantly from the general trends; they have remarkably
high Sr contents of 1.68 and 2.60 mg/L, respectively, and
plot near the Sr/Cl seawater line.
The relationship between Sr and Cl in the deep
groundwater from the Cretaceous-Eocene limestone re-
sults in a high correlation coefficient, i.e., r2=0.93. Shal-
low groundwaters exhibit some variations in the Cl and
Sr contents which may indicate young groundwater with
multiple sources of Sr and Cl. However, groundwater
samples from both Quaternary and Neogene aquifers
have positive correlations between Cl and Sr, with corre-
lation coefficients of r2=0.76 and 0.84, respectively
(Fig. 2).
Surface waters from the seaward parts of the Volta
River and from the Keta Lagoon have high EC values
and high Cl and Sr contents, indicating a mixture of
fresh water and seawater (Table 1).
Hydrogen and Oxygen Isotopes
The hydrogen and oxygen isotopic compositions of
groundwaters, surface water from the Volta River estuary
and Keta Lagoon, and seawater from the Gulf of Guinea
DOI 10.1007/s100400000122
194
Table 1 Electrical conductivi- 87Sr/86Sr
ty, Cl and Sr contents, and Boreholes EC Cl Sr 1/Sr
87Sr/86Sr ratio of deep and shal- (µS/cm) (mg/L) (mg/L) (L/mg)
low groundwater and surface 1996/1998 1996/1998 1996 1996 1996
water from the Keta Basin
and seawater from the Gulf of Deep groundwater in weathered Dahomeyan gneiss
Guinea B1 Akatsi 1,140/1,170 155/165 0.48 2.08 0.714008
B2 Akatsi 1,060/1,030 165/161 0.65 1.54 0.713757
B3 Akatsi 589/565 134/132 0.39 2.56 0.712992

Dug wells EC Cl Sr 1/Sr 87Sr/86Sr

(µS/cm) (mg/L) (mg/L) (L/mg)
1996/1998 1996/1998 1996 1996 1996

Shallow groundwater in continental Neogene sediments

B6 Atsiame 1,576/1,742 355/392 0.92 1.09 0.712196
B11 Klikor 665/738 110/126 0.23 4.35 0.711762
B12 Klikor 725/803 132/148 0.22 4.55 0.711717
B13 Klikor 1,246/1,376 180/203 0.48 2.08 0.711643
B18 Dabala 1,074/1,184 215/238 0.42 2.38 0.711094
B19 Dabala 1,155/1,275 260/287 0.43 2.33 0.712258
C5 Badeku 2,090/2,305 425/474 0.94 1.06 0.711640
C6 Badeku 491/635 92/104 0.29 3.45 0.711662
C7 Kasseh 920/1,005 332/364 0.63 1.59 0.712004

Boreholes EC Cl Sr 1/Sr 87Sr/86Sr

(µS/cm) (mg/L) (mg/L) (L/mg)
1996/1998 1996/1998 1996 1996 1996

Deep groundwater in Cretaceous-Eocene limestones

B4 Anyoko-Kpota K55 1,071/1,084 118/115 0.62 1.61 0.708406
B5 Anyoko K18 1,219/1,196 120/129 0.68 1.47 0.708232
B7 Tsiame K34 873/864 111/105 0.54 1.85 0.708482
B8 Avenor-Peme K33 972/992 105/99 0.38 2.63 0.708873
B9 Klikor 732/724 126/131 0.88 1.14 0.707936
B10 Klikor K44 734/741 105/102 0.47 2.13 0.708563
B14 Agbozume K43 723/725 112/116 0.56 1.79 0.708514
B15 Denu K46 4,970/5,065 1,505/1,525 1.68 0.60 0.708468
B16 Aflao K41 863/854 152/147 0.95 1.05 0.708043
B17 Aflao-Averne K42 890/998 165/170 1.05 0.95 0.708059
B22 Anloga 11,900/11,300 3,475/3,410 2.60 0.38 0.708658
B24 Keta K50 983/967 122/105 0.39 2.56 0.709736

Dug wells EC Cl Sr 1/Sr 87Sr/86Sr

(µS/cm) (mg/L) (mg/L) (L/mg)
1996/1998 1996/1998 1996 1996 1996

Shallow groundwater in Quaternary marine sand and gravel

B20 Srogboe 755/842 135/151 0.48 2.08 0.708902
B21 Whuti 874/965 290/322 0.46 2.17 0.708996
B23 Anloga 802/885 170/188 0.36 2.78 0.708985
B25 Keta 467/522 65/73 0.23 4.35 0.708902
B26 Tegbi 877/972 195/218 0.55 1.82 0.709052
B27 Tegbi 268/301 87/101 0.29 3.45 0.708861
C2 Ada Foah 727/815 130/147 0.27 3.70 0.708939
C3 Ada Foah 1,055/1,165 330/365 0.75 1.33 0.709163
C4 Anyakor 267/298 55/63 0.25 4.00 0.708908

Locations EC Cl Sr 1/Sr 87Sr/86Sr

(µS/cm) (mg/L) (mg/L) (L/mg)

Seawater from the Gulf of Guinea and Surface water from the Volta River and Keta Lagoon
Seawater:
Ada Foah 48,800 19,000 8.10 0.12 0.709261
Keta 48,900 19,000 8.10 0.12 0.709248
Volta River:
Al Ada Foah 42,800 13,100 6.9 0.15 0.709244
A2 Ada Foah 731 190 0.19 5.26 0.711142
785 215 0.23 4.22 0.710860

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 195
Table 1 (continued) 87Sr/86Sr
Locations EC Cl Sr 1/Sr
(µS/cm) (mg/L) (mg/L) (L/mg)

A3 Big Ada 106 16 0.10 10.0 0.713539

110 16 0.12 8.68 0.712860
A4 Sogakope 70 14 0.11 9.1 0.713456
Keta Lagoon:
A5 Anyanui 24,100 9,200 4.0 0.25 0.709287
A6 Woe 13,900 5,450 2.3 0.43 0.709310

are shown in Table 2; the relationships between δ2H and

δ18O are shown in Fig. 3. The hydrogen and oxygen iso-
topic compositions of precipitation and infiltrating wa-
ters are controlled by various physical factors, e.g., lati-
tudinal and altitudinal effects, intensity and duration of
rainfall, temperature, and evaporation and condensation
in recharge and drainage areas (Dansgaard 1964; Clark
and Fritz 1997). Unfortunately, no isotopic precipitation
data are available for the study area. The general meteor-
ic relationship between the oxygen and hydrogen iso-
topes has been described by the global meteoric water
line (GMWL) with the equation:
δ2Hvsmow=8δ18Ovsmow+10 (1)
(Craig 1961; vsmow: Vienna Standard Mean Ocean Wa-
ter). Fig. 3 Relation between δ18O and δ2H for groundwaters in the
Acheampong and Hess (2000) report isotopic data for Keta Basin, surface water from the Volta River and Keta Lagoon,
rainfall from various locations in the southern Voltaian and seawater from the Gulf of Guinea. The global meteoric water
Sedimentary Basin of Ghana, and these plot close to the line (GMWL) (Craig 1961) and local meteoric water line (LMWL)
global meteoric water line. However, Akiti (1987) estab- for the Accra plains (Akiti 1987) are shown for reference
lished a local meteoric water line (LMWL) for the Accra
Plains of southeast Ghana close to the study area, and
this line is described as:
δ2Hvsmow=7.86δ18Ovsmow+13.6 (2)
The slope is close to that of the global meteoric water
line, but the line has a larger y-intercept. The two mete-
oric water lines (GMWL and LMWL) are shown for ref-
erence in Fig. 3. The plots of the isotopic compositions
of groundwaters in this study are generally below the
LMWL and scatter around the GMWL.
Seawater collected close to the seashore west of Ada
Foah and off Keta (Fig. 1b) has an isotope composition
very close to 0(VSMOW) for both isotopes, as reported for
modern oceanic seawater (Fig. 3). Apparently, at these
sites there is no influence of fresh water from the Volta
River. Surface waters collected at the delta outlet close
to Ada Foah, and from various sites in the estuary and
the Keta Lagoon have a strong marine influence on the Fig. 4 Relation between δ18O and δ2H for deep groundwater in
isotopic compositions; δ2H and δ18O values are slightly Cretaceous-Eocene limestone and Proterozoic Dahomeyan gneiss
depleted but close to zero. Surface waters from the Volta in the Keta Basin. The global meteoric water line (GMWL) (Craig
1961), local meteoric water line (LMWL) for southeastern Ghana
River collected at a greater distance from the sea (Big (Akiti 1987), and local groundwater–seawater line (LGSL) are
Ada and Sogakofe, Fig. 1b) have isotopic compositions shown for reference. B15 Anloga and B22 Denu are deep wells in-
that are strongly affected by evaporation; they are signif- fluenced by seawater intrusion
icantly enriched in 18O and 2H (Fig. 3).
The isotopic compositions of groundwater from deep
wells are shown in Fig. 4. Most values scatter around the

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196
Table 2 Oxygen- and hydrogen-isotope compositions in shallow and deep groundwater and surface water from the Keta Basin and sea-
water from the Gulf of Guinea. Water samples collected during the rainy season of 1996 and during the dry season of 1998

Boreholes Rainy season 1996 Dry season 1998 Dug wells Rainy season 1996 Dry season 1998

δ 2H δ18O δ 2H δ18O δ 2H δ18O δ 2H δ18O

Deep groundwater in weathered Dahomeyan gneiss Shallow groundwater in Quaternary marine sand and gravel
B1 Akatsi –13.2 –2.97 –14.2 –3.20 B20 Srogboe –19.1 –3.66 –18.3 –3.46
B2 Akatsi –10.9 –2.90 –13.3 –3.08 B21 Whuti –15.8 –3.14 –14.6 –2.86
B3 Akatsi –13.6 –2.83 –13.4 –2.76 B23 Anloga –15.5 –2.75 –13.8 –2.42
B25 Keta –22.1 –3.96 –16.9 –3.22
Dug wells Rainy season 1996 Dry season 1998 1326 Tegbi –17.3 –3.18 –15.4 –2.81
B27 Tegbi –17.8 –3.36 –14.9 –2.85
δ 2H δ18O δ 2H δ18O C2 Ada Foah –15.6 –2.86 –15.2 –2.75
C3 Ada Foah –12.0 –2.28 –12.4 –2.11
Shallow groundwater in Neogene continental sediments C4 Anyakor –15.8 –2.91 –14.9 –2.75
B6 Atsiame –16.8 –3.29 –15.1 –3.23
B11 Klikor –19.3 –3.57 –16.4 –3.03 Locations Rainy season 1996 Dry season 1998
B12 Klikor –16.1 –3.50 –15.3 –3.38
B13 Klikor –17.5 –3.85 –17.1 –3.55 δ 2H δ18O δ 2H δ18O
B18 Dabala –16.4 –3.13 –10.7 –2.04
B19 Dadala –15.0 –3.48 –13.7 –3.24 Seawater from the Gulf of Guinea and Surface water from the Vol-
C5 Badeku –14.3 –2.61 –12.6 –2.41 ta River and Keta Lagoon
C6 Badeku –15.2 –3.21 –14.4 –3.12
C7 Kasseh –14.5 –2.78 –12.9 –2.55 Seawater:
Ada Foah 0.2 –0.04
Boreholes Rainy season 1996 Dry season 1998 Keta 0.1 –0.02

δ 2H δ18O δ 2H δ18O Volta River:

Al Ada Foah –0.8 –0.12 –0.1 –0.15
Deep groundwater in Cretaceous-Eocene limestone A2 Ada Foah –2.3 –0.86 –0.6 –0.22
B4 Anyoko-Kpota K55 –15.3 –3.52 –16.1 –3.50 A3 Big Ada –3.2 –1.01 –2.9 –0.95
B5 Anyoko K18 –16.2 –3.54 –16.3 –3.59 A4 Sogapoke –3.2 –1.04
B7 Tsiame K34 –16.7 –3.40 –17.9 –3.48
B8 Avenor-Peme K33 –19.0 –3.40 –18.6 –3.37 Keta Lagoon:
B9 Klikor –19.4 –3.45 –20.8 –3.51 A5 Anyanui –2.3 –0.63
B10 Klikor K44 –18.3 –3.53 –18.6 –3.46 A6 Woe –1.7 –0.41
B14 Agbozume K43 –18.3 –3.46 –18.6 –3.42
B15 Denu K46 –13.7 –2.55 –13.9 –2.49
B16 Aflao K41 –20.7 –3.83 –19.8 –3.81
B17 Aflao-Aveme K42 –21.1 –3.82 –21.4 –3.88
B22 Anloga –10.5 –1.90 –10.2 –2.00 anic seawater. The relationship is described by the equa-
B24 Keta K50 –16.5 –3.46 –15.4 –3.37 tion:
δ2Hvsmow=5.3δ18Ovsmow+0.7 (3)
The isotopic compositions of shallow groundwaters from
dug wells in Quaternary and Neogene aquifers are shown
GMWL, but groundwater samples from aquifers in the in Fig. 5. A large number of samples from dug wells
Dahomeyan gneiss are slightly enriched in 18O and 2H in completed in Neogene aquifers plot between the LMWL
comparison to most groundwater samples from the Cre- and the GMWL. However, the majority of samples have
taceous-Eocene limestone aquifers. a wide range in isotopic compositions below the GMWL
The deep groundwaters have only small variations, and plot along an evaporation line or mixing line that is
and no significant differences exist in the isotopic com- described by the regression line:
positions between water samples collected in the dry
season of 1998 and those collected in the rainy season δ2Hvsmow=4.96δ18Ovsmow−0.96 (r2=0.92) (4)
of 1996 (Fig. 4 and Table 2). The two boreholes in the This line is very close to the local seawater–groundwater
Cretaceous-Eocene limestone aquifers, B15 Denu and mixing line (eq. 3) with respect to slope as well as y-in-
B22 Anloga, which yield saline groundwater, are signifi- tercept, and the two lines are not statistically distinguish-
cantly enriched with respect to both isotopes and fit well able.
with the local seawater–groundwater mixing line. The Some shallow groundwater samples from dug wells
local seawater–groundwater mixing line for the lime- are characterized by relatively high Cl contents. Figure 6
stone aquifer is calculated based on the arithmetic mean shows the relationship between Cl contents and δ18O for
of the isotopic compositions for deep groundwater ob- shallow groundwater. A considerable scatter in the val-
tained from the Cretaceous-Eocene limestone aquifers ues is observed, but two categories may be considered.
with Cl contents less than 200 mg/L (δ18O=–3.51‰, Group 1 (Fig. 6a) includes groundwater samples from
δ2H=–17.9‰) and the local isotopic composition of oce- both Quaternary and Neogene aquifers with isotopic

Hydrogeology Journal (2001) 9:190–201 DOI 10.1007/s100400000122


Fig. 5 Relation between δ18O and δ2H for shallow groundwaters
in Quaternary marine sediments and Neogene continental sedi-
ments in the Keta Basin. The global meteoric water line (GMWL)
(Craig 1961) and local meteoric water line (LMWL) (Akiti 1987)
are shown for reference. RL Regression line for data points below
GMWL
compositions that plot along the mixing line below
the GMWL. These samples have a positive correlation
between Cl and 18O isotopic compositions. Group 2
(Fig. 6b) includes groundwater samples from Neogene
aquifers with stable-isotope compositions that plot be-
tween the GMWL and LMWL. These samples have rela-
tively constant oxygen-isotope compositions, but their Cl
contents range from 50 to approximately 400 mg/L. The
initial Cl contents for the shallow groundwater are esti-
mated to be 50–100 mg/L, on the basis of the Cl contents
recorded in the most isotopically depleted groundwater
samples.
Fig. 6 Relation between Cl and δ18O for shallow groundwaters in
Quaternary and Neogene aquifers in the Keta Basin. a Group 1
groundwaters with isotopic compositions that plot along a mixing
line below the global meteoric water line. b Group 2 groundwaters
with isotopic compositions that do not deviate significantly from
the global meteoric water line
Hydrogeology Journal (2001) 9:190–201
197
Strontium 87Sr/86Sr Isotopes
The Sr isotope compositions of the groundwater in the
Keta Basin primarily reflect the geology of the forma-
tions in the aquifers. The 87Sr/86Sr ratios of dissolved Sr
in groundwater are mainly controlled by water–rock in-
teractions and, therefore, the isotopic compositions of
the strontium-bearing minerals in the host rock (Faure
1986). Proterozoic igneous rocks that contain Sr-bearing
minerals like K-feldspar, hornblende, and mica high in
radiogenic 87Sr have high 87Sr/86Sr ratios, i.e., >0.710.
The Sr-isotope composition of groundwater that is in ap-
proximate chemical equilibrium with marine sedimenta-
ry sequences is related to the marine Sr-isotope seawater
curve (Burke et al. 1982; Veizer 1989; Veizer et al.
1999). Therefore, the Sr isotope compositions of ground-
water in aquifers composed of marine sedimentary se-
quences to some extent reflect the stratigraphic age of
the geological formation (Jørgensen and Holm 1994,
1995).
The Sr-isotope ratios of groundwater and surface wa-
ter in the Keta Basin have a wide range, from low
87Sr/86Sr ratios of approximately 0.7079 to relatively
high 87Sr/86Sr ratios of 0.7140, as shown in Fig. 7 and
Table 1. The water samples analysed are grouped into
five categories, according to recharge area and type of
aquifer:
1. Surface water, including samples of fresh water from
the Volta River, brackish water from the Keta Lagoon,
and seawater collected from the Gulf of Guinea west
of Ada Foah and off the town of Keta (Fig. 1b). The
Sr-isotope compositions of surface water vary widely
and include 87Sr/86Sr ratios of 0.7130 for the fresh riv-
er water, approximately 0.7112 in the seaward parts
of the estuary and from the Keta Lagoon, and 0.7092
for the seawater samples. The 87Sr/86Sr ratio of 0.7092
corresponds to the isotope ratio normally reported for
oceanic seawater (Faure 1986; Veizer et al. 1999).
The 87Sr/86Sr ratios and the reciprocal Sr concentra-
tions of the surface-water samples correlate signifi-
cantly to a mixing line (r2=0.99) with seawater as one
end member. The other end member is unknown, but
the high 87Sr/86Sr ratios (>0.710) indicate that it is
DOI 10.1007/s100400000122
198
meteoric water highly influenced by Sr released from
Proterozoic crystalline basement rocks in the catch-
ment.
2. Groundwater samples collected from three deep wells
in Akatsi, which tap an aquifer of fractured and
weathered Proterozoic Dahomeyan gneiss (Fig. 7 and
Table 1). This groundwater has much more radiogenic
Sr than any other groundwater sampled in the study
area and is characterized by 87Sr/86Sr ratios of
0.7130–0.7140.
3. Shallow groundwaters from dug wells completed in
aquifers consisting of Neogene continental deposits of
sandy clay, sand, and gravel. The 87Sr/86Sr ratios are
high, ranging from 0.7111–0.7126. Considerable vari-
ation exists in the values, and no evident correlation
exists between the 87Sr/86Sr ratios and the reciprocal
Sr concentrations in the groundwater (Fig. 7). Fur-
thermore, no differences exist in Sr-isotope composi-
tions between the two groups considered in Fig. 6.
4. Shallow groundwater from dug wells completed in
Quaternary marine sand and gravel on the coastal
strip. This groundwater has relatively constant
87Sr/86Sr ratios of 0.7092–0.7089, which correspond
to the Sr-isotope compositions of the Quaternary ma-
rine strata (Hodell et al. 1991). The significant corre-
lation (r=0.76) between the isotope ratios and the re-
ciprocal Sr contents indicates a mixing line with the
isotopic composition of seawater (0.7092) as one end
member (Fig. 7). The other end member probably
represents the 87Sr/86Sr ratios of marine Sr released
from dissolved biogenic carbonate in the Quaternary
marine sediments.
5. Deep groundwater obtained from boreholes in Creta-
ceous-Eocene limestone aquifers. The 87Sr/86Sr ratios
range from 0.7079–0.7089 (Fig. 7 and Table 1). The
majority of the samples have 87Sr/86Sr ratios with a
significant correlation (r2=0.83) to the reciprocal Sr
contents, indicating a well-defined mixing line. The
lowest 87Sr/86Sr ratio obtained is approximately
0.7079, which corresponds to the isotopic composi-
tion of Early Tertiary marine limestone Sr as one end
member (Burke et al. 1982). This is in accordance
with the age of the younger part of the limestone se-
quence which is of Cretaceous-Eocene age (Gill
1969). However, the steep slope of the mixing line
does not exclude an end member with a slightly low-
er isotopic composition, which would be in accor-
dance with the expected 87Sr/86Sr ratio of the forma-
tion. Two deep wells, B15 Denu and B22 Anloga, de-
viate significantly from the majority of sampled
boreholes, with 87Sr/86Sr ratios of 0.7085 and 0.7087,
respectively, and relatively high Sr contents. The
87Sr/86Sr ratios and the reciprocal Sr contents for
these two boreholes fit a mixing line with isotopic
composition of Early Tertiary marine limestone Sr as
one end member and isotopic composition of oceanic
seawater (0.7092) as the other end member, indicat-
ing a strong influence from intruding seawater (Fig. 7
and Table 1).
Hydrogeology Journal (2001) 9:190–201
Fig. 7 Relation between 87Sr/86Sr ratio and 1/Sr for deep and shal-
low groundwater and surface water from the Keta Basin and sea-
water from the Gulf of Guinea
Discussion
The oxygen- and hydrogen-isotope compositions of
groundwaters from the Keta Basin are slightly isotopi-
cally enriched in comparison to groundwater studied in
the Upper West Region and Upper East Region of Ghana
(Kortatsi and Sekpey 1993), but they are similar to the
compositions of groundwater in the southern Voltaian
Sedimentary Basin (Acheampong and Hess 2000), in the
surroundings of Accra (Akiti 1987), and those reported
from coastal basins at the same latitude in West Africa,
e.g., in Nigeria (Loehnert 1988). Furthermore, the
groundwater from the Keta Basin is slightly isotopically
enriched in comparison to the isotopic compositions
of groundwater from other West African countries lo-
cated in more continental realms like Niger, Burkina
Faso, Mali, and Senegal (Bison et al. 1989; Joseph and
Aranyossy 1989; Mbonu et al. 1993). The geographical
distribution of isotopic compositions is believed to be
the result of a combination of latitudinal and altitudinal
effects. However, the observed differences in isotopic
compositions between the aquifers of Cretaceous-Eocene
limestone and the Dahomeyan gneiss (approximately
1‰ δ18O and 4‰ δ2H, respectively) are not readily ex-
plained. The reason cannot be the result of altitudinal/
latitudinal effects, but it may be due to natural variations
in the regional and local climate.
Groundwater plays a vital role in the domestic water
supply and in farming economies in the Keta Basin. The
extensive distribution of groundwater with relatively
high chloride contents in the Keta Basin is therefore of
particular concern. Deep aquifers in the Dahomeyan
basement and Cretaceous-Eocene limestone yield pota-
ble water of relatively high quality after applying careful
well-construction methods and after consideration of a
proper development strategy. The isotopic variations
within the two deep aquifers are relatively small and no
significant seasonal effects are observed, indicating a
long residence time for these groundwaters (Fig. 4).
DOI 10.1007/s100400000122

However, highly saline deep groundwater observed in
Cretaceous-Eocene aquifers demonstrates that precau-
tions must be taken in near-coastal aquifers. The oxygen-
and hydrogen-isotope compositions of saline groundwa-
ter correlate with the local groundwater–seawater line,
and the distribution of 87Sr/86Sr ratios suggests that the
major source of saline groundwater is the result of a sig-
nificant modern marine influence.
The quality of shallow groundwater is of much more
concern. Many water wells and dug wells have been
abandoned due to increasing salinity problems over time.
However, all the listed dug wells are presently in use for
domestic water supply, though these groundwaters have
a wide range of Cl contents, with concentrations of as
much as ~500 mg/L, which exceeds the limit for a satis-
factory potable water supply.
The oxygen- and hydrogen-isotope compositions of
shallow groundwater samples have larger variations than
do the compositions of deep groundwater, which is to
some extent also reflected in fluctuations between wet
and dry seasons (Figs. 4 and 5, Table 2 ). These varia-
tions are probably the result of local recharge events and
evaporation from the unsaturated zone, which mean that
seasonal fluctuations are preserved in shallow groundwa-
ter reservoirs. However, some dug wells are constantly
open, which means that evaporation also takes place
from the free water surfaces.
Most groundwater samples from shallow aquifers
have isotopic compositions that are below the GMWL
and plot along a straight mixing line that is close to the
local seawater–groundwater mixing line. However, the
Cl contents observed in shallow groundwaters are sub-
stantially below the concentrations expected according to
seawater intrusion and, consequently, evaporative en-
richment has to be considered. The maximum average
evaporation loss expressed by the present data can be
calculated according to a method demonstrated by Clark
and Fritz (1997). To calculate the evaporative loss, the
local evaporation slope, the initial isotopic composition,
and the annual mean temperature for the area need to be
known. The slope of the local evaporation line reflects
the influence of varying local conditions but depends
largely on relative humidity. The slope of the regression
line is calculated from equation (4) to be ~5, which cor-
responds to a relative humidity (h) of approximately
70% (Gonfiantini 1986). This figure is in accordance
with the reported humidity of 65–75% (Dickson and
Benneh 1995). The kinetic effect (∆ε), in terms of hu-
midity between the boundary layer (bl) and water vapour
(v), can be described with respect to δ18O by the follow-
ing relationship:
∆ε18Obl-v=14.2(1-h)‰ (5)
(Gonfiantini 1986), i.e., for shallow groundwater in the
Keta Basin, ∆ε18O=14.2(1−0.70)=4.3‰. The mean an-
nual temperature for the Keta Basin is 27 °C. The frac-
tionation factor α for 18O between water and vapour at
this temperature corresponds to 103lnα18Ow-v~9.1‰
(Notations are: ln, natural logarithm; w,water; v, vapour;
Hydrogeology Journal (2001) 9:190–201
199
Majoube 1971). The overall enrichment for evaporation
under these conditions is εtotal=εv-l+∆εv-bl=−9.1+(−4.3)=
−12.7‰ The initial δ18O composition is estimated to be
–5‰ on the basis of the intersection between the LMWL
and the regression line, and the evaporative enrichment
is therefore approximately 3‰ (see Fig. 5).
The loss from evaporation can be modelled according
to Rayleigh distillation:
ε18Ototal*lnƒ=δ18Ogw−δ18Oprec=3.00‰ (6)
yielding a residual water fraction ƒ of 0.79 and thus an
average evaporation loss of approximately 21%. Howev-
er, this value indicates that evaporation loss alone cannot
account for the excess of Cl of more than ×4 in compari-
son to the initial composition of 50–100 mg/L estimated
for shallow groundwaters. Furthermore, the scatter in the
Cl and δ18O distributions shown in Fig. 6 indicates mul-
tiple sources of Cl.
A source that can contribute to the Cl budget in sur-
face water and shallow groundwaters is sea-spray and
aerosols in coastal regions exposed to onshore winds
(Berner and Berner 1987; Herut et al. 1993). The prox-
imity of the sea and the occurrence of large open sand
flats, typically associated with brackish-water lagoon en-
vironments, could lead to wind- and rain-borne marine-
derived salts deposited in the topsoils, which could be
the cause of the relatively high Cl and Sr contents ob-
served in many dug wells. The presence of dissolved
modern marine Sr in shallow groundwaters is comple-
mented by the Sr-isotope data obtained from the Quater-
nary aquifers on the coastal strip. A significant correla-
tion exists between 87Sr/86Sr ratios and reciprocal Sr, in-
dicating a mixing line with the isotopic composition of
modern marine Sr as one end member (Fig. 7).
The Cl and δ18O distributions, currently observed in
shallow groundwaters (group 1), have no appreciable
difference with regard to aquifer type, suggesting that
some sort of marine influence, e.g., brackish water from
the lagoons and/or seaspray, is most likely also responsi-
ble for the enhanced Cl contents recorded in Neogene
aquifers. However, the strontium isotope compositions
of shallow groundwater from Neogene aquifers do not
explicitly indicate a modern marine influence but rather
multiple sources of dissolved Sr. The relatively high
87Sr/86Sr ratios and the scatter of the values indicate that
most of the dissolved Sr includes a variety of highly ra-
diogenic weathering products from the Proterozoic crys-
talline basement rocks. The shallow Neogene aquifers
are located farther inland in the lagoonal environments
of the Keta Basin. Furthermore, surface water from the
Volta River and brackish water from the Keta Lagoon are
characterized by variable but relatively high 87Sr/86Sr ra-
tios, which may also contribute to the strontium-isotope
signature of the shallow groundwater in Neogene aqui-
fers.
DOI 10.1007/s100400000122
200
Summary and Conclusions
Strontium-isotope compositions in groundwater and sur-
face water in the Keta Basin primarily reflect the litho-
logical characteristics of aquifers and catchments as a re-
sult of weathering processes and water–rock interactions.
In addition, however, strontium-isotopes are sensitive in-
dicators of modern marine influence. Thus, strontium-
isotope distributions as well as oxygen- and hydrogen-
isotope compositions demonstrate the mixing of fresh
water and seawater in the Keta Lagoon and the Volta
River estuary.
The oxygen- and hydrogen-isotope compositions of
samples collected from shallow and deep groundwater
plot along a seawater mixing line or evaporation line.
High Cl contents (>1,500 mg/L) in deep groundwater
suggest seawater intrusion as the major reason for saline
groundwater in these wells, and this evidence is comple-
mented by a well-defined mixing line for strontium iso-
topes with seawater as one end member.
The salinity of shallow groundwater generally does
not exceed 500 mg/L Cl. Evaporative loss alone cannot
explain the excess of Cl in these aquifers. A marine in-
fluence is significant in the Quaternary near-coastal
aquifers, as indicated by a well-defined mixing line for
strontium isotopes with modern seawater as one end
member. A similar straightforward relationship with re-
spect to the strontium-isotope distributions cannot be
demonstrated in groundwater collected from Neogene
aquifers, which are located in the lagoonal environment
in the central part of the Keta Basin, probably because of
multiple sources of dissolved strontium in these aquifers
as well as in the brackish water of the lagoons. However,
brackish lagoon water and/or seaspray and aerosols are
probably the sources of the enhanced Cl contents in shal-
low Neogene aquifers.
The interpretations derived from environmental iso-
topes of shallow and deep groundwaters and surface wa-
ters from the Keta Basin demonstrate that the multi-iso-
tope approach provides a useful supplement to tradition-
al hydrochemical analyses in order to identify the origin
and sources of saline groundwaters.
Acknowledgements This project was supported by DANIDA, the
Danish International Development Authority, grant no. 104.Dan.
8L/300. The mass-spectrometer facilities were funded by the
Danish Natural Science Foundation. Reviews by F.J. Pearson and
H.N. Waber greatly improved the manuscript.
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