Sustain. Water Resour. Manag.

DOI 10.1007/s40899-017-0107-6

ORIGINAL ARTICLE

δ18O and δ2H characteristics of rainwater, groundwater

and springs in a mountainous region of Ghana: implication
with respect to groundwater recharge and circulation
Abass Gibrilla1 · Dickson Adomako1 · Geophrey Anornu2 · Samuel Ganyaglo1 ·
Tibor Stigter3 · Joseph R. Fianko1 · ShivePrakash Rai4 · Andrews Ako Ako Jr5

Received: 3 February 2015 / Accepted: 13 March 2017

© Springer International Publishing Switzerland 2017

Abstract In this study, the characteristics of δ2H and
δ18O in rainwater, groundwater and spring water have been
used to understand the groundwater recharge dynamics
in the Amedzofe area (one of the highest human habita-
tion in Ghana). The local Meteoric Water Line (LMWL)
using all the rainfall events gave an equation with the best
fit line of δ2H = 7.32 δ18O + 8.20 (n = 113; r2 = 0.94).
Heavier rainfall events greater than 10, 20 and 30 mm fur-
ther orient the slope closer to the Global Meteoric Water
Line (GMWL). The data showed that the isotopic compo-
sitions of the rainwater in the area are mainly influenced
by the rainfall amount with temperature having minimal
effect. All the spring water and most of the groundwater
plot around the GMWL, implying they are of meteoric
origin. The Chloride Mass Balance (CMB) and δ18O shift
methods suggest annual mean recharge rate of 160.43 and
125.79 mm/year representing 10.70 and 8.39% of annual
rainfall, respectively. The estimated mean recharge rate
for the spring was 317.51 mm/year and 300.68 mm/year
* Abass Gibrilla
gibrilla2abass@yahoo.co.uk
1
Nuclear Chemistry and Environmental Research Center,
National Nuclear Research Institute, GAEC, Box LG 80,
Legon‑Accra, Ghana
2
Department of Civil Engineering, Kwame Nkrumah
University of Science and Technology (KNUST), Private
Mail Bag University Post Office, Kumasi, Ghana
3 natural resources. This is because locked in every drop of
Department of Water Science and Engineering, UNESCO-
IHE Institute for Water Education, P.O. Box 3015,
2601 DA Delft, The Netherlands
4
Hydrological Investigation Division, National Institute
of Hydrology, Roorkee 247 667, India
5
Hydrological Research Centre Yaounde´, P.O. Box 4110,
Yaounde´, Cameroon
representing 26.46 and 25.06% of annual rainfall for CMB
and δ18O shift methods, respectively. Rainfall stable iso-
topes from Kpando and Amedzofe gave an altitude effect
of 0.17/100 m and altitude of recharge of the springs from
+724.00 to +788.61 m amsl. The stable isotopes data iden-
tified two distinct moisture sources, isotopically enriched
local moisture (evaporated surface water bodies and evapo-
transpiration water vapour flux from vegetation) and iso-
topically depleted moisture source from the Atlantic Ocean.
The results further showed that significant groundwater
recharge in the study area takes place in the months of
March, June and August.
Keywords Stable isotopes · Rainwater · Recharge ·
Altitude of recharge · Groundwater · Ghana
Introduction
The development of groundwater resources in Ghana for
domestic, industrial and agricultural purposes has con-
tributed immensely in the socio-economic development
and eradication of water-borne diseases in many rural
communities in the country. In a world facing severe chal-
lenges to the environment and availability of fresh water,
sustainable exploitation of water resources has become
a global concern. Nuclear technology has been proven as
a vital tool to help manage and maximise the use of these
water is vital information that can be explored to establish
its source, movement and threat to pollution. The manage-
ment of water resources using environmental isotopes has
witnessed several research efforts worldwide, eg in Europe
and Americas (Dincer et al. 1970; Mook et al. 1974; Rodhe
1984; Kennedy et al. 1986), in Asia (Sklash et al. 1976;

13
Vol.:(0123456789)

Saha et al. 2013), in Australia (Banks et al. 2011; Cart-
wright et al. 2012) and in Africa (Acheampong and Hess
2000; Fontes and Olivry 1976; Goni 2006; Oga et al. 2008;
Onugba and Aboh 2009; Nyarko et al. 2010; Adomako
et al. 2010a, b; Wirmvem et al. 2014).
The stable isotopes of hydrogen (2H) and oxygen (18O)
are rare components of the water molecule ­ (H2O) that
fall as rain and snow each year over a watershed (Rozan-
ski et al. 1993; Clark and Fritz 1997; Kendall and Cald-
well 1998; Gat 2010) and differ temporally and spatially
(Dansgaard 1964; Jouzel et al. 1997). The variability of the
isotopic composition of precipitation is primarily driven
by global and regional trends. This is as a result of suc-
cessive isotopic fractionation processes occurring at each
phase of the hydrological cycle due to the differences in
the physical properties of the isotopic species, HDO and
­H218O, and of H ­ 216O (Dansgaard 1964; Kendall and Doc-
tor 2011). Atmospheric moisture and precipitation acquires
unique isotopic ratio of heavy to light as a result of isotopic
fractionation processes, thereby, making their isotopic ratio
an ideal tracers of water (Gat 2010; Rozanski et al. 1993;
Fontes 1980). This unique behaviour of stable isotopes
makes them a powerful tool in hydrological and climate
studies (Liu et al. 2008). They offer a broad range of pos-
sibility for studying processes within the water cycle. Sta-
ble isotopes data from these components of the hydrologic
cycles can provide useful information on the origin of water
vapour, condensation and precipitation history, groundwa-
ter recharge mechanism, relationship between the various
sources of water (rainwater, spring water, groundwater and
waters from different aquifers). This nearly ideal conserva-
tive behaviour has also led to the development of method-
ologies to estimate recharge from stable isotopes (Allison
et al. 1984; Saxena and Dressie 1984). In addition to the
wide and successful applications in the hydrological dis-
cipline, previous studies (e.g., Hobson 1999; Hobson and
Wassenaar 1996) and (Bricout 1982; Dunber 1982; Kelly
et al. 2002) had successfully applied the stable hydrogen
and oxygen to ecological and agricultural studies in tracing
wildlife migration and authenticating agricultural products
respectively.
Stable isotope studies of groundwater in Ghana date
back to the early 1980s (Akiti 1980). Since then, several
uncoordinated and scattered data on stable isotopes on
groundwater in different parts of the country have been
generated (Acheampong and Hess 2000; Jorgensen and
Banoeng-Yakubu 2001; Pelig-Ba 2009; Adomako et al.
2010a, b; Gibrilla et al. 2010; etc). These studies have
attempted to characterize different aspects of the hydro-
logical conditions of specific basins in the country. The
findings have been diverse in their utility of the isotope
tracers. However, all these relevant studies require that
the stable isotope compositions of rainwater in the study
13
Sustain. Water Resour. Manag.
region be fully investigated in advance. This is because
rainwater is the primary and vital source of water to
groundwater and surface water and an important input
parameter for any hydrological studies using isotopes.
Hence, the compilation of long-term records of stable
isotope compositions of hydrogen and oxygen in rain-
water is an important pre-requisite for atmospheric and
hydrological studies in any given study.
Despite the abundant rain in Ghana and the global
effort since 1961 by the International Atomic Energy
Agency (IAEA) and World Meteorological Organization
to coordinate and conduct a worldwide survey of isotopic
compositions for precipitation known as the Global Net-
work of Isotopes in Precipitation (GNIP), data on rain-
water stable isotopes in Ghana and many other African
countries are rare and sporadic. The main aim of the net-
work is to provide an invaluable long-term global data-
base for subsequent isotopic studies. Currently, the only
well coordinated and systematic sampling of rainwater
in Ghana include the march 2007 to September 2008 in
Koforidua in the Eastern region (Adomako et al. 2010a)
and June to July 2007, April to October 2008 and May to
August 2009 in Kubore and May to October 2005, April
to August 2008 and May to July 2009 in Pwalugu in the
Upper East region from the Global Network of Isotopes
in Precipitation (IAEA/WMO database on the web: http://
isohis.iaea.org). In recent years, with the acquisition of
DLT 100 Los Gatos Research liquid water isotope ana-
lyser in the late 2010 by the National Nuclear Research
Institute of the Ghana Atomic Energy Commission has
made stable isotope analysis less expensive. Therefore,
several studies on rainwater, groundwater and surface
water have been carried out (Ganyaglo et al. 2010; Kaka
et al. 2011; Nafisa et al. 2012; Saka et al. 2013; Yidana
2013) and large scale sampling campaign of groundwater
and surface water is currently ongoing (WRC 2010, 2011,
2012, 2013).
The Gemi Mountains is one of the highest mountains in
Ghana and is located next to Amedzofe—a compact set-
tlement, 36 km North-West of Ho, the capital of the Volta
Region. It is believed to be the highest place of human
habitation in Ghana and that one cannot walk a distance
of 20 m in any direction without descending or climbing
a slope. The area is endowed with abundant rain, surface
water and several spring water sources which are the major
sources of water for the inhabitants. The demand for pota-
ble water is expected to increase due to population growth;
hence, knowledge of the groundwater recharge and dynam-
ics is essential in understanding the aquifer systems and
the management options for the groundwater resources.
Despite the several groundwater stable isotopes studies in
Ghana, data on chemical and isotopic studies on groundwa-
ter and spring water in the Amedzofe area is scarce.
Sustain. Water Resour. Manag.
Given the major and important role of stable isotopes
in hydrological studies and the lack of such data in Ghana,
an attempt has been made to revive the GNIP programme,
and for the first time collect and analyse rainfall events for
δ18O and δ2H in the Amedzofe area of the Volta region of
Ghana. This study is the first in Ghana to provide three (3)-
year records of stable isotope data of rainwater on event
basis. The main purpose of the study were to (1) generate
baseline data of 18O and 2H to contribute to the GNIP data-
base, (2) determine the monthly variability of the isotopic
composition in rainfall (3) determine the factors influenc-
ing the isotopic signature of the rainfall, (4) compare the
values obtained with other continental stations in the lit-
erature. The study will also assess groundwater recharge
mechanism, circulation pattern and estimate recharge.
Fig. 1  Map of the study area
Materials and methods
Study area
The area is part of the Dayi river basin and lies between
latitude 7°19′N and 6°38′0″N and longitude 0°39′E and
0°17′E. It is bounded to the east by the Togo border, to the
north by the Hohoe Municipality, to the west by the Volta
lake and to the south by the Ho municipality (Fig. 1). The
area is characterized by a series of highlands and adjacent
lowlands, scattered hills and mountain ranges of varied
lengths and heights. It is made up of two different types of
vegetative zones. The north-western and eastern section of
the basin is forested land (characterized by closed canopy
of branches and little undergrowth mainly on the slopes of
the Akwapim-Togo-Attakora mountain ranges), which are
gradually being modified by agricultural activities. The
northern section of the basin is savannah woodland, and
characterized with grass and scattered trees like acacia and
bamboo (WRC 2011).
13

The climate of the area is controlled by the southwest
monsoon winds and the dry harmattan winds from the
Atlantic Ocean and the Sahara Desert respectively. The
basin is has a bi-modal rainfall regime with mean tem-
perature ranging from 22 to 32 °C while annual rainfall
of the lower plains averages about 1100–1300 mm and
approaches 1400–1600 mm in the higher ranges. (Fig. 2).
Average mean humidity for Amedzofe is between 70 and
96% (0600 h) and between 53 and 87% at 1500 h (WRC
2011). The mountainous settlements like Amedzofe and
Vane have very low temperatures during some parts of the
year and are often referred to as the “local winter” of the
Volta Region. The two main rivers in the area are Alabo
which is ephemeral and Dayi which is perennial.
The basin is underlain by Sedimentary Precambrian
crystalline igneous and metamorphic rock (basement com-
plex) unit of Ghana. These units are made up of three geo-
logical formations namely, Buem, Dahomeyan and the
Togo Series Fig. 1 (Gill 1969; Gyau-Boakye et al. 2008).
The Buem Structural Unit which occupies about 50% of
the basin is highly folded along a more or less northeast-
southwest line, and is located west of the Togo Structural
Unit (Kesse 1985). Typical rock types forming aquifer in
the area are shale, sandstone, and volcanic rocks with sub-
ordinate limestone, tillite, grit, and conglomerate. The
Dahomeyan Structural Unit is made up of basically crystal-
line gneiss and migmatite, with subordinate quartz schist,
biotite schist and sedimentary rocks. The gneiss is gener-
ally massive with few fractures. The Togo Structural Unit
consists of metamorphosed arenaceous and argillaceous
200
Amedzofe
180
Rainfall Amt(mm)
160
140
120
100
80
60
40
20
0 0
Months
Rainfall Amt Min Temp(oC)
Fig. 2  Monthly minimum and maximum temperature distributions and rainfall amount from 2000 to 2010 in the study area (Data source: Ghana
Meteorological Agency)
13
Sustain. Water Resour. Manag.
sedimentary strata. The rock types include indurated sand-
stone, quartzite, quartz schist, shale, phyllite, sericite-schist
and silicified-limestone (Kesse 1985).
The success rate for developing wells in the Dahomian
is about 36% and average borehole yield range from 0.3 to
0.8 L s (10.8–28.8 m3/d). The Dahomeyan rocks have mean
transmissivity of 4.5 m2/d with a range of 0.3–42 m2/d
(Darko and Krásny 2003). The Togo Series and Buem For-
mation have negligible primary porosity or permeability
but contain openings along joints, bedding, and cleavage
planes. Where these openings are extensive, good supplies
of groundwater can be developed from boreholes. Springs
frequently occur along the flanks of hills where quartzites
are in contact with argillaceous rocks of the valleys. Weath-
ering in the quartzite produces unconsolidated alluvium
of sand and quartzite fragments that are a source of good
supplies of groundwater from shallow wells. The success
rate for obtaining water from boreholes in the Togo Series
and Buem Formation is about 88%. The average yield from
these boreholes is about 2.6 L s with a range of 0.2–7 L
s (Gyau-Boakye et al. 2008). The higher-yielding bore-
holes in this area probably tap large fractured systems or
fault zones. Transmissivity values range between 0.9 and
43 m2/d with an average of 8.0 m2/d. Boreholes are drilled
to an average depth of 65 m in sandstone.
Sampling
One hundred and fifty-eight samples were collected
between 2011 and 2013 (113 rainwater samples, 38
250 40
Kpando
Monthly average Temperature (oC)
35
35
Rainfall Amount (mm)
200
Monthly Average Temp(oC)
30
30
25 25
150
20 20
100
15 15
10 10
50
5 5
0 0
Months
Max Temp(Oc) rainfall amount Min Temp (oC) Max Temp (oC)
Sustain. Water Resour. Manag.
groundwater samples and 7 spring-water samples). The
location of rainwater, groundwater and spring-water
samples are shown in Fig. 1. Rainwater samples for sta-
ble isotopes were taken on event basis in 60 ml steri-
lised HDPE polyethylene bottles. The samples were then
labelled (date and rainfall amount) and stored away from
light in a cool dry place. Samples were taken for analy-
sis at the end of each month. Representative groundwa-
ter and spring water samples were also taken in 60 ml
HDPE bottle from the boreholes (fitted with pumps
mainly used for domestic activities). Prior to sampling,
the boreholes were purged of stagnant water. At the
time of sampling, most of the wells were in use, hence
purging lasted about 5–10 min. Special care was taken
to ensure that no air bubbles were trapped in the bot-
tles and all the bottles were filled to the brim to avoid
evaporation.
Analytical methods
All samples were analyzed for δ18O and δ2H in the Iso-
tope Hydrology laboratory of the National Nuclear
Research Institute of the Ghana Atomic Energy Com-
mission. The δ18O and δ2H values of the water samples
were measured using LGR DLT-100. All oxygen and
hydrogen isotopic analyses are reported in standard delta
(δ) notation versus Vienna Standard Mean Ocean Water
(VSMOW2) IAEA (1992).
(1)
( )
𝛿 = Rsample ∕Rv - smow − 1 × 1000
18 16
where Rsample and Rv-smow represent either the O/ O or
2 1
H/ H ratios of the sample and standard.
The uncertainty of the measurement was determined
by repeated analysis of international reference materi-
als V-SMOW2, GISP, and SLAP2 as well as lab inter-
nal standards (n = 20). The analytical precision is ±0.2%
for δ18O, and ±2% for δ2H, respectively. The volume-
weighted mean of δ-values (δ18O and δ2H) for each
month was computed according to the following formula
(IAEA 1992):
∑
(Pi × 𝛿 18 Oi )
18
𝛿 Omonthly = ∑ (2)
Pi
(Pi × 𝛿 2 Hi )
∑
𝛿 2 Hmonthly = ∑ (3)
Pi
where Pi denotes the amount of each individual precipita-
tion samples, δ 2Hi and δ 18Oi denotes the isotopic compo-
sition of each rainfall event.
Results and discussions
Stable isotopes of (δ18O and δ2H) characteristics
of the rainfall events and Monthly Weighted Mean
in the study area
The statistical summary of the isotopic composition of the
rainfall events from 2011 to 2013 at Amedzofe are pre-
sented in Table 1 while Fig. 3a–c shows the time series plot
of 18O, 2H and d-excess. The δ18O values for the individual
rainfall events range from −8.77 to 2.73 with mean value of
−2.81 while δ 2H range from −59.27 to 21.14 with mean
value of −12.13. There is no marked seasonal variation of
δ18O and δ 2H values, but generally more depleted values
are associated with months with higher rainfall from April
to July and from September to October. The relationship
between δ 2H and δ18O in precipitation called the Global
Meteoric Water Line (GMWL) was first reported by Craig
(1961) as δ 2H = 8δ18O + 10. Craig (1961) model proposed
that, the slope of 8 is controlled by the ratio between iso-
tope equilibrium fractionation factors of hydrogen and oxy-
gen, while the intercept of 10 is controlled by evaporation
processes in the origin of the water vapour. Three and half
decades later, Rozanski et al. (1993) proposed a new rela-
tionship for stable isotopes in modern precipitation as δ 2H
= 8.2δ18O + 11.27. These are global averages, hence may
differ slightly from area to area due to differences in geo-
graphical and meteorological factors (water vapour source,
storm trajectory, climate condition, rainfall variation). The
plot of δ18O and δ 2H of all the rainfall events together with
modified Global Meteoric Water Line (GMWL) defined by
δ2H = 8.17 δ18O + 11.27 (Rozanski et al. 1993) and Local
Meteoric Water Line (LMWL) of Accra plains define by
δ2H = 7.86 δ18O + 13.62 (Akiti 1980) shows a positive lin-
ear correlation (Fig. 4). The equation for the best fit line
representing the LMWL for the Amedzofe area is:
𝛿 2 H = 7.32𝛿 18 O + 8.20 R2 = 0.94; n = 113 (4)
( )
It was observed from Fig. 4 that, most of the samples
analysed clustered around the Global Meteoric Water Line
(GMWL). The rainwater data from the study area describe
a local meteoric line (LMWL), with a slope and intercept
slightly lower than the slope of 8.2 and intercept of 11.27
Table 1  Statistical summary of stable isotopes in the area
Rain amount (mm) δ18O‰ δ2H‰ d-excess
Min 2.20 −8.77 −59.27 −7.13
Max 134.50 2.73 21.14 19.04
Mean 22.18 −2.81 −12.13 10.13
SD 18.46 2.16 16.41 4.32
Variance 340.62 4.67 269.39 18.66
13
 Sustain. Water Resour. Manag.

Fig. 3  Stable isotopes data of

18/03/2011
26/03/2011
21/04/2011
08/05/2011
12/06/2011
20/06/2011
05/07/2011
15/07/2011
27/08/2011
24/09/2011
03/10/2011
12/10/2011
28/02/2012
30/04/2012
15/05/2012
05/06/2012
02/03/2013
30/03/2013
18/04/2013
30/04/2013
18/05/2013
01/06/2013
02/07/2013
11/07/2013
22/07/2013
09/09/2013
20/09/2013
08/10/2013
rainfall samples (a) δ18O values
(b) δ2H values and (c) d-excess
a 4.00

2.00

0.00

δ18O (‰)
-2.00

-4.00

-6.00

-8.00

-10.00

b 30.00
20.00
10.00
0.00
δ2H (‰)

-10.00

-20.00

-30.00

-40.00

-50.00

-60.00

-70.00

c 25.00

20.00

15.00
d-excess (‰)

10.00

5.00

0.00

5.00-

10.00-

Fig. 4  The isotopic composi-

tions of rainfall samples and LMWL
30.00
their resultant LMWL in the δ2H =7.32 δ18O + 8.20; R2=0.94
study area

10.00
Aki Line
δ2H =7.86 δ18O + 13.62
δ 2H ‰

-10.00 GMWL
δ2H =8.17 δ18O + 11.27

-30.00
Rainwater
Linear (Rainwater)
Linear (GMWL)
-50.00
Linear (Aki Line)

-70.00
-10.00 -8.00 -6.00 -4.00 -2.00 0.00 2.00 4.00

δ18O ‰

13
Sustain. Water Resour. Manag.

of the GMWL. This deviation in the slope suggests that (1)
the rain formation process in the study area do not occur
under conditions close to isotopic equilibrium, i.e., that
most of the rainfall events occur at relative humidity lower
than 100%. (2) the rainwater drops have undergone partial
evaporation before arrival at the land surface (Plata 1994).
In Ghana, similar slopes have been reported with limited
rainwater stable isotopes data as shown in Table 2. This
suggests that a common moisture source and hydrologi-
cal cycle is responsible for the rainfall in most part of the
country.
The deuterium excess (d-excess) defined by
d-excess = δ2H − 8δ18O (Dansgaard 1964) is the intercept
of the δ2H vrs δ18O relationship. Generally, d excess varies
from place to place due to the differences in evaporation
conditions of the air mass sources (Gat 1980). Figure 3c
gives the temporal variation of d-excess in the individual
rainfall events in the study area. The d-excess varies from
−7.13 to 19.04 with a mean value of 10.13. The d-excess
values in Fig. 3c shows little seasonal variation in the area.
However, the varied intercept obtained from the various
studies (Table 2) reflects the varied climatic effects such as
re-evaporation and relative humidity in each of the study
area.
The effect of secondary evaporation has been shown
to be higher for light rains. This is because, once the air
column is water-saturated, such secondary evaporation
is diminished. Therefore, the slope of the meteoric water
lines for heavy rainfall will be close to that of the GMWL.
Thus, meteoric water lines were developed for heavy rain-
fall events greater than 10, 20 and 30 mm.
𝛿 2 H = 7.54𝛿 18 O + 9.28 n = 81; R2 = 0.93 Rain > 10 mm
( )
(5)
𝛿 2 H = 7.57𝛿 18 O + 9.38 n = 48; R2 = 0.94 Rain > 20 mm
( )
(6)
𝛿 2 H = 7.52𝛿 18 O + 9.13 n = 26; R2 = 0.96 Rain > 30 mm
( )
The slopes of these meteoric water lines are 7.54, 7.57
and 7.52 for rainfall greater than 10, 20 and 30 mm, respec-
tively. The results show no significant differences between
the slopes of rainfall greater than 10, 20 and 30 even though
they differ from the slope of all the rainfall events. Mook
(2006) stated that the threshold of precipitation for the sec-
ondary evaporation to have an effect is 20 mm. Similarly,
Clark and Fritz (1997) found that, excluding rainfall events
less than 20 mm yields the slope of the LMWL around 7.8
almost similar to the equilibrium value of 8. Even though,
the threshold of 20 mm gave the best value closer to 8, the
threshold 10 mm was found to be equally good an applica-
ble for the study area.
The Monthly Weighted Mean (MWM) of δ18O from
March 2011 to October 2013 range from −5.94 to −2.23
while δ2H range from −37.31 to −4.53 with respective
mean values of −3.55 and −17.42. Due to the absence of
Local Monthly Weighted Mean Line (LMWML) stable iso-
topes in Ghana and West Africa except the work of Wirm-
vem et al., 2014 in Cameroon, we compared our data with
different continental station found in literature regarding
the LMWML (Table 3). Careful study of Table 3 shows
that, the slope of our dataset is similar to the slope of most
of the studies. However, Vodila et al. 2011; IAEA (2010);
Baresic et al. 2006; Vreca et al. 2006; Krajcar-Bonic et al.
1998; Jacob and Sonntag 1991 reported lower intercept val-
ues which were attributed to intense secondary evaporation,
origin and the trajectory of the precipitation. It worth men-
tioning here that, Wirmvem et al. (2014) reported a slope
quite close to our data in the Ndop plain in Cameroon.
This suggests that, rainfall in Ndop plain and our study
area have similar origin and trajectory of the air moisture
mainly from the Atlantic Ocean. This is also not surpris-
ing because the two areas have the following characteristics
in common (1) humid tropical equatorial climate (2) high
altitudes (3) annual rainfall above 1000 mm (4) close to the
Atlantic Ocean.
The extent of below-cloud secondary evaporation affect-

(7) ing rainfall events using the differences between the slope
of δ2H and δ18O of individual rainfall and calculated

Table 2  δ18O and δ 2H equations developed in different studies in Ghana

Site Basin d (m asl) Equation n References

Aburi-Accra Densu 427–35 δ2H = 7.86 δ18O + 13.61 8 Akiti (1980)

S Voltain – δ2H = 7.02 δ18O + 4.3; r2 = 0.98 8 Acheampong and Hess (2000)
Tamale Volta 151 δ2H = 6.9 δ18O − 0.19; r2 = 0.91 15 Pelig-ba (2009)
Koforidua Densu 350 δ2H = 7.7 δ18O + 11.1; r2 = 1 31 Adomako et al. (2010a, b)
Accra Densu 35 δ2H = 6.2 δ18O + 11; r2 = 0.89 11 Saka et al. (2013)
Tamale Volta 151 δ2H = 7.28 δ18O + 4.77 23 Yidana (2013)
Amedzofe Dayi 737 δ2H = 7.32 δ18O + 8.20 (r2 = 0.94) 113 This study

n number of samples, d altitude, S Voltain southern voltain

13
 Sustain. Water Resour. Manag.

Table 3  Comparison of Year Location Slope Intercept R2 Data no References

the LMWL developed from
amount weighted monthly data 2011–2013 Amedzofe 7.97 10.82 0.95 20 This paper
of the study area with some
2012 Ndop plain 7.93 13.26 0.99 11 Wirmvem et al. (2014)
continental stations
2001–2009 Debrecen 6.55 −7.74 0.89 107 Vodila et al. (2011)
1976–1996 Zagreb 7.90 6.90 0.99 194 Krajcar-Bonic et al. (1998)
1976–1996 Ljubljana 8.10 11.10 0.99 149 Krajcar-Bonic et al. (1998)
1976–2003 Zagreb 7.70 4.50 0.96 270 Baresic et al. (2006)
1980–2003 Zagreb 7.80 5.70 0.98 271 Vreca et al. (2006)
1981–2003 Ljubljana 8.20 10.70 0.99 255 Vreca et al. ((2006)
2001–2003 Ljubljana 8.00 9.20 0.99 36 Vreca et al. ((2006)
1981–1988 Heidelberg 8.06 5.90 0.99 96 Jacob and Sonntag (1991)
1960–2007 Vienna 7.29 0.19 0.96 534 IAEA (2010)

amount weighted mean was suggested by Peng et al.
(2007). They propose that, the higher the difference in
the slope and intercept, the greater influence of second-
ary evaporation. In this study, the amount weighted mean
regression line defined by δ2H = 7.97 δ18O + 10.84 (n = 20;
R2 = 0.95) have both slope and intercept higher than the
instead of March 2013, the month with the highest temper-
ature 26.75 °C). The monthly surface temperatures (T) and
δ18O during the study period is described by the following
least-squares-fit linear regression.
𝛿 18 O = 0.09TMonthly − 5.75 R2 = 0.012 (8)
( )

event base regression line in Eq. 4. The intercepts of the
two regression lines have a difference of 2.61 suggesting
some degree of secondary evaporation in the area. This
is consistent with the data reported by Peng et al. (2007)
despite some studies doubting it applicability in a continen-
tal climate (Vodila et al. 2011).
Atmospheric temperature and rainfall amount effect
on the stable isotopes
Several factors influence the distributions of stable isotopes
in rainwater. They include altitude, latitude, temperature
and rainfall amount (Gat 2010). Isotopic fractionation that
occurs during condensation and evaporation is inversely
related to temperature (Mazor 2004; Mook 2006). As a
result, precipitations normally have higher isotopic val-
ues during warmer summers and lower values during
colder winters. The coefficient of the relationship between
∆δ18O/∆T are very useful for paleoclimatic application
of stable isotopes as they reflect the long-term linkage
between the isotopic relations between climate and rain-
fall in any given area (Darling et al. 2005; Rozanski et al.
1993). Several authors have reported ∆δ18O/∆T slope rang-
ing from 0.2 to 0.45‰/°C in the temperate Europe (Darling
et al. 2003; Vreca et al. (2006); Vodila et al. 2011).
In the tropical Amedzofe mountains, the monthly
weighted average δ18O do not exhibit these typical sea-
sonal variations in isotopic composition (Fig. 5).The most
depleted sample was collected during October 2011 (δ18O
= −5.94, δD = −37.31, average temperature 23.91 °C),
while the most enriched sample was taken in May 2011
(δ18O= −2.23, δD= −7.65, average temperature 24.86 °C)
Although temperature is an important factor control-
ling the variation in the isotopic content of rainfall, our
data show that there is no clear relationship between tem-
perature measured on the ground and the rainwater isotopic
compositions in the area. This could be due to the narrow
range in temperature (about ~4 °C) in the Amedzofe area.
The weak correlation of δ18O and temperature (R2 = 0.012)
suggests that temperature is not the dominant factor con-
trolling the isotope fractionation. Similar observation was
also made by Fonte and Olivry (1976) on the relationship
between temperature and the rainwater stable isotopes in
the tropical region of Cameroon. For this reason, the rela-
tion between δ18O and rainfall amount was also examined.
In this case, there is a very good correlation between aver-
age monthly rainfall (P) and δ18O and described by the lin-
ear regression,
𝛿 18 O = −0.012PMonthly − 1.96 R2 = 0.61 (9)
( )
This indicates that the amount effect is the dominant
process controlling the isotopic composition of the rain-
fall in the area. Secondly, the observed inverse relation in
Eq. (9) between the monthly rainfall amount and weighted
monthly δ18O (Fig. 5) is in agreement with amount effect
characteristic of tropical low latitude rains (Dansgaard
1964; Rozanski et al. 1993). Yurtesever and Gat (1981)
also found that, high latitude continental areas experi-
ence more pronounced temperature effect while in tropical
regions, the amount effect is more dominant. Similar obser-
vations were also made in some parts of West Africa such
as Cameroon (Wirmvem et al. 2014; Njitchoua et al. 1999;
Gonfiantini et al. 2001), Nigeria (Mbonu and Travi 1994;

13
Sustain. Water Resour. Manag.

0 28.00

Average Monthly Temperature (oC)

Weighted Monthly Avera ge 18O
-1 Avera ge Monthly Tem pera ture 27.00

Weighted Monthly δ 18O -2

26.00

25.00
-3
24.00
-4
23.00
-5
22.00

-6 21.00

-7 20.00
350

300

250
Rainfall (mm)

200

150

100

50

Months

Fig. 5  Temperature, δ18O and amount effects of rainfall in the Amedzofe mountains

Goni et al. 2001) and Chad (Goni 2006). Even though, our
results is in agreement with other studies, the amount effect
accounted for only about 62% of the variation of the δ 18O
in the rainfall. Hence, other factors such as altitude effect
are also likely to have significant effect on the rainfall δ 18O
in the area.
Origin of groundwater and spring water using δ18O
and δ2H isotopes compositions
The stable isotopes composition of the groundwater in the
area is presented in Table 4. The distribution of δ18O ranges
from −3.42 to −1.53 with a mean value of −2.61 and δ2H
ranges from −14.07 to −6.75 with a mean value of −10.77.
The spring water δ18O ranges from −3.26 to −2.42 with a
mean value of -2.82 and δ2H ranges from −14.68 to −10.06
with a mean value of −11.40. The regression lines for the
spring water and groundwater are.
Spring:𝛿 2 H = 8.33 𝛿 18 O + 10.70
Groundwater:𝛿 2 H = 2.16 𝛿 18 O − 5.41 (11)
Considering all the groundwater data, there was a wide
variation in the stable isotopes as compared to the spring
water. Furthermore, the slope and intercept of the regres-
sion line of the spring water are close to the slope and
intercept of the regression line of the monthly weighted
mean rainfall. The plot of the stable isotopes data on the
δ18O–δ2H diagram (Fig. 6a) showed that, most of the
groundwater and all the spring water plot on the GMWL
and LMWL. This implies that, they are of meteoric origin.
It also indicates that, the effect of evaporation is minimal
especially in the spring water, perhaps due to rapid and fast
infiltration during recharge and the spring water dynamics
are mainly controlled by the rainfall events. However, few
groundwater samples (about 7) mainly from southern part
of the study area plot in the upper right part of the Fig. 6a.
This group of samples are characterized by enrichment in
isotopes, suggesting that they have undergone evapora-
tion. This observation is a typical characteristic of shallow
groundwater and groundwater receiving recharge from sur-
face water.
Estimation of groundwater recharge and recharge
mechanism in the Amedzofe area
(10) Groundwater use is of fundamental importance and often
the key to economic and social development in many parts
of the world, particularly in areas where surface water sup-
plies are unreliable and poorly distributed. The evaluation
of the groundwater resources involves several factors of
which the groundwater recharge is a key. An understand-
ing of the recharge processes, natural recharge rate and
sustainable yield are basic requirement for the efficient

13
 Sustain. Water Resour. Manag.

Table 4  Stable isotopes composition of groundwater in the study area

Sample location Sample id North East E δ18O‰ δ2H‰ Cl R(Cl) RCl(%P) R (18O) R18O(%P)

GOVIEFE KOWU GK 6.70972 0.33462 116 −2.44 −11.54 195.94 21.93 1.46 35.29 2.35
GOVIEFE AGORDOME GA 6.71508 0.33765 171 −2.36 −11.35 119.96 35.81 2.39 30.30 2.02
AGATE AG 6.73910 0.34982 187 −2.77 −10.51 57.98 74.09 4.94 77.85 5.19
HAVE H 6.75128 0.35540 163 −2.76 −14.07 67.98 63.20 4.21 74.63 4.98
HAVE EP SCHOOL H1 6.75493 0.35956 171 −2.53 −12.99 135.96 31.60 2.11 42.14 2.81
HAVE EP SCHOOL H2 6.75617 0.35985 177 −2.51 −12.73 129.96 33.06 2.20 40.85 2.72
ANDO NO 2 AN 6.81610 0.33126 132 −3.12 −13.23 41.99 102.32 6.82 334.84 22.32
ANDO NO 2 AN1 6.81671 0.33315 121 −3.10 −12.60 19.99 214.87 14.32 293.94 19.60
ANDO NO 2 AN2 6.81665 0.33407 118 −3.04 −13.16 45.99 93.42 6.23 208.75 13.92
VAKPO SEC SCHOOL VA 6.84289 0.29893 121 −2.94 −13.32 16.00 268.58 17.91 139.15 9.28
VAKPO SEC SCHOOL VA1 6.84232 0.29812 130 −2.68 −10.69 14.27 301.10 20.07 60.23 4.02
VAKPO SEC SCHOOL VA2 6.84445 0.29730 123 −2.89 −10.47 31.99 134.29 8.95 115.02 7.67
VAKPO SEC TECH VA3 6.85998 0.28617 161 −2.66 −10.05 25.99 165.28 11.02 58.17 3.88
VAKPO CONGO VA4 6.86051 0.29225 145 −2.95 −12.78 23.99 179.06 11.94 145.20 9.68
VAKPO ADEABRA VA6 6.85603 0.28535 160 −2.76 −12.85 17.99 238.74 15.92 75.61 5.04
NYANGBO ODUMASI NO1 6.79970 0.37253 178 −3.11 −10.73 23.99 179.06 11.94 317.61 21.17
NYANGBO ODUMASI NO2 6.79982 0.37254 177 −2.92 −10.96 23.99 179.06 11.94 130.32 8.69
NYAGBO AGODOME NA 6.81399 0.37449 154 −2.67 −9.943 25.99 165.28 11.02 59.14 3.94
NYAGBO GAGBEFE NG 6.81519 0.37270 145 −2.91 −9.595 33.99 126.39 8.43 121.43 8.10
AVATIME BIAKPA BK 6.84164 0.42129 429 −3.36 −10.91 10.00 429.73 28.65 819.73 54.65
AVATIME BIAKPA BK1 6.84187 0.42134 426 −3.42 −11.23 16.00 268.58 17.91 629.05 41.94
AKOME GBORGAME AA 6.81456 0.46477 303 −2.43 −11.34 19.99 214.87 14.32 34.89 2.33
AKOME AGATE AA1 6.81184 0.46332 317 −2.50 −11.14 12.00 358.11 23.87 40.18 2.68
AKOME AGATE AA2 6.81086 0.46435 302 −2.69 −7.67 27.99 153.48 10.23 62.64 4.18
DZOLO KPUITA JK JUNC 6.78789 0.44091 278 −2.29 −9.18 23.99 179.06 11.94 26.75 1.78
DZOLO KPUITA SCH DK1 6.78569 0.44303 273 −2.03 −9.71 10.00 429.73 28.65 17.85 1.19
DZOLOKPUITA HOSP DK3 6.78536 0.44386 276 −1.98 −11.55 19.99 214.87 14.32 16.66 1.11
DZOLOKPUITA HOSP DK2 6.78539 0.44381 277 −2.00 −11.43 29.99 143.24 9.55 17.12 1.14
DZOLO GBORGAME DG 6.77002 0.48228 257 −2.11 −6.748 127.96 33.57 2.24 19.93 1.33
DZOLO GBORGAME DG1 6.76998 0.48233 258 −1.88 −7.538 147.95 29.04 1.94 14.61 0.97
DZOLOGBORGAME DG2 6.76767 0.48048 249 −1.71 −7.833 133.96 32.07 2.14 11.88 0.79
DZOLOGBORGAME DG3 6.76761 0.48050 248 −1.53 −7.667 95.97 44.76 2.98 9.80 0.65
AKORVIEFE AKO 6.75729 0.48104 227 −2.03 −9.59 91.97 46.71 3.11 17.85 1.19
MATSE DZOLO MD 6.73384 0.47601 206 −2.64 −8.68 8.00 298.01 19.87 54.87 3.66
MATSE ANDO MA 6.71773 0.47134 195 −2.36 −11.21 10.00 243.82 16.25 30.30 2.02
MATSE MT 6.69710 0.48320 219 −2.77 −8.198 51.98 82.64 5.51 78.30 5.22
MATSE MTI 6.69412 0.48329 209 −3.35 −13.23 33.99 126.39 8.43 391.48 26.10
Min 116.00 −3.42 −14.07 8.00 21.93 1.46 9.80 0.65
Max 429.00 −1.53 −6.75 195.94 429.73 28.65 819.73 54.65
Mean 210.00 −2.60 −10.77 52.05 160.43 10.70 125.79 8.39
SD 79.47 0.47 1.91 49.38 111.49 7.43 176.13 11.74

E elevation (m), Cl chloride (mg/l), R(Cl) recharge using CMB, RCl(%P) recharge percentage of annual precipitation using CMB, R (18O)
recharge using 18O, R18O(%P) recharge percentage of annual precipitation using 18O

and sustainable management of the groundwater resources.
(Chand et al. 2005; Scanlon and Cook 2002; Scanlon et al.
2002; Sanford 2002; Gonfiantini et al. 1998).
The chloride mass balance (CMB) method has been used
extensively for estimating groundwater recharge especially
in arid and semi-arid areas worldwide due to the conserva-
tive nature of the chloride ion (Gee et al. 2004; Scanlon
et al. 2002; Tindall and Kunkel 1999). Quite recently,
Oteng Mensah et al. (2014) use CMB method to determine
recharge in a tropical environment. The estimates were

13
Sustain. Water Resour. Manag.

Fig. 6  δ18O and δ2H relation- a 0

ship of a weighted monthly
mean of rainwater, three-year -5 Aug
weighted mean of rainwater,
Mar
groundwater and the spring -10
water b weighted monthly mean Jun Feb
of rainwater and three-year -15

δ2H‰
weighted mean of rainwater, Jul
-20 Sep May

Apr
-25
Weighted Monthly Mean Rainwater Isotopes
Three Years Weighted Mean Rainwater Isotopes
-30 Groundwater
Oct
Springs
-35
-5.5 -5 -4.5 -4 -3.5 -3 -2.5 -2 -1.5
δ18 O‰

b 0
y = 7.705x + 9.877
-5 Aug
R² = 0.937
Three years weighted mean Mar
-10
Jun Feb
-15
δ2H‰

Jul
-20 Sep May
Apr
-25
Weighted Monthly Mean Rainwater Isotopes
-30 Three Years Weighted Mean Rainwater Isotopes
Oct
-35
-5.5 -5 -4.5 -4 -3.5 -3 -2.5 -2 -1.5 -1

δ18 O‰

found to be consistent with evaporation rates computed
from stable isotope data of groundwater and surface water.
The result was also found to be consistent with groundwa-
ter recharge estimation using numerical model calibration.
In the study area, under the assumptions that chloride
is the conservative ion and rainwater the only source of
chloride (Cl), a mass balance of chloride in precipitation,
surface runoff and groundwater is obtained. The balance
can be represented mathematically as shown in Eq. 10
(McNamara 2005; Sumioka and Bauer 2004):
PCp = RCgw + QCp (12)
where P is annual precipitation (mm); Cp is concentra-
tion of chloride in rainfall (mg/l); R is annual groundwater
recharge (mm); Cgw is concentration of chloride in ground-
water (mg/l); Q is annual surface runoff (mm).
Neglecting surface runoff, the terms in Eq. 10 can be
re-arranged to calculate the groundwater recharge as:
PCp
R=
Cgw
Chloride concentrations in rainwater from 2011 to
2013 ranged from 2 to 14 mg/l. Chloride concentration
measured on 26th September, 2011 was exceptionally
high (14 mg/l). This was taken to be an outlier and was
not considered in the estimation of the overall recharge.
Eliminating the outlier, chloride concentration in rainwa-
ter ranged from 2 to 6 mg/l, with a mean and standard
deviation of 3.76 and 1.39 mg/l, respectively. However,
in calculating the recharge, the weighted average chlo-
ride concentration of 3.58 mg/l based on 113 rainwater
sample collected in the area was used. This is to account
for account seasonal fluctuation in rainwater composition.
The long-term mean annual rainfall in the study area of
1500 mm was used. The overall groundwater recharge for
the study area was calculated based on the chloride val-
ues obtained for the individual wells.
The results show that the groundwater recharge in the
area ranged from 21.93 to 429.73 mm, representing 1.46
to 28.65% of the mean annual rainfall. The overall mean
groundwater recharge was estimated to be 160.43 mm, rep-
resenting 10.70% of the long-term mean annual rainfall
(13) (Table 4). The estimated recharge is close to the recharge
of 0.9–21% in a similar tropical environment estimated by
Oteng Mensah et al. (2014).
Recharge can also be estimated using oxygen isotopic
composition of groundwater and rainwater and associated

13

rainfall data. It is assume that, the groundwater oxygen iso-
topic composition is the weighted average of rainwater that
actually infiltrates to the water table. As shown in Fig. 6a,
the groundwater samples plot around the LMWL. The
observed deviation can be used to understand the recharge
mechanism in the area. Allison et al. (1984) proposed an
empirical relationship to determine recharge in mm/year
through thick sand using the δ18O shift from Global Mete-
oric Water Line. This equation was later modified by Yin
et al. (2011) for small vadose zone with shallow water table
as
6
𝛿 18 O Shift = √ (14)
R A=
where R is Recharge, δ 18O Shift is the deviation of the
individual groundwater isotopic values from the weighted
mean rainwater isotopic value.
The rainwater oxygen isotopic data from the Amed-
zofe sampling station gave a weighted average rainwater
δ 18O value −3.45 over the period of 2011 to 2013. This
gives δ18O Shift in the order of 0.2 to 1.9‰. The resultant
groundwater recharge ranges from 9.80 to 819.73 mm/year
with average value of 125.79 mm/year. This represents 0.65
to 54.65% with average value of 8.39% of annual rainfall.
To determine the suitability of the δ18O shit method in
the study area, a comparison of the recharge obtained using
the CMB method in the study area was made. The results
showed that the two methods are generally in agreement
regarding potentially high and low recharge areas (Fig. 7).
Although there are some disagreements regarding the
recharge values for some locations, the average recharge
estimated by the two methods and the spatial distribution of
the recharge are very close and similar.
Estimation of spring water recharge, altitude effect
and altitude of recharge
Springs are important components of the hydrosphere
where groundwater flows onto the surface. The Amedzofe
community depends mainly on spring water for domes-
tic activities. As shown in Fig. 6a, the spring water stable
isotopes falls very close to the GMWL indicating that the
springs receive direct recharge and the hydrology of the
springs are mainly controlled by local rainfall with little
evaporation during recharge. The estimated recharge using
the CMB method ranged from 61.39 to 784.63 mm/year
with average recharge value of 317.51 mm/year (Table 5).
This represents a recharge rate of 5.12 to 65.39% with mean
value of 26.46% of annual rainfall. The δ18O Shift method
gave recharge estimate of 33.93 to 997.23 mm/year with a
mean value of 300.68 mm/year representing 2.83 to 83.10%
with mean value of 25.06% of annual rainfall. It can be
13
Sustain. Water Resour. Manag.
observed that, the two estimates produced mean values that
are relatively close.
The altitude effect (systematic decrease of stable iso-
tope composition with increasing altitude) was determined
using the relationship between δ 18O vrs altitude (Fig. 8).
This effect has been widely used by several authors as a
tool to determine groundwater-recharge zones (Payne and
Yurtsever 1974; Fontes and Olivry 1976; Gonfiantini et al.
2001; Yurtsever and Gat 1981; Gasparini et al. 1990; Kat-
tan 1997b). The calculated altitude effect using δ18O of the
WMM of −3.45 and −2.62 from Amedzofe and Kpando
using Eq. 15 gave an altitude effect of 0.17/100 m.
Δ(𝛿 18 O)
(15)
Δz
where A is altitude effect, ∆(δ18O) is change isotope com-
position of rainwater and ∆Z is change in elevation.
This value varies slightly with the value of −0.13‰
obtained by Akiti (1980) from rainfall in Accra (35 m)
and Aburi (427 m) above mean sea level. However, studies
by Fontes and Olivry (1976) on the Cameroon mountains
yielded an altitude effect of −0.16‰ per 100 m which is
close to the result obtained in this study. Using the calcu-
lated altitude effect and the δ18O of rainwater, a relation-
ship between δ18O of rainwater and elevation was obtained
as:
𝛿 18 O‰ = −0.013(‰) × Elevation (m) + 6.992 (16)
The estimated altitudes of the recharge of the springs
from this relation are given in Table 5 and Fig. 8. The esti-
mated recharge elevation in the Amedzofe area range from
+724.00 to +788.61 with a mean value of +755.12 m amsl.
Inter‑relationship between rainwater, groundwater
and spring water and implication for groundwater
utilization in the Amedzofe area
Stable isotopes data have been used to understand the
inter-relationships between rainwater, groundwater and
the spring water in the Amedzofe area. The effect of
meteorological processes on stable isotopes in water
provides a fingerprint of their origin. This fingerprint
is fundamental in investigating the origin of groundwa-
ter (Clark and Fritz 1997). Most of the groundwater and
all the spring water plot along the GMWL and LMWL,
this indicates that present day rainfall is recharging the
groundwater and the springs. A plot of weighted monthly
δ2H and δ18O showed two distinct moisture sources
(Fig. 6b). The first group comprising Feb, Mar, Jun and
August rains plotted in the upper portion. This suggests
that, they may originate from isotopically enriched local
moisture (evaporated surface water bodies) and evapo-
transpiration water vapour flux from vegetation. This is
Sustain. Water Resour. Manag.
Fig. 7  Comparison and spatial distribution of recharge by the CMB and δ18O shift method
not surprising, the study area is very close to the Volta
Lake, one of the largest manmade lakes in the world and
is characterised by tropical rain forest vegetation. The
second group is characterized by depleted stable isotopes
and plot at the lower part of the line. This group com-
prises Apr, May, Jul, Sep and Oct rains. This observa-
tion suggests that the rainfall moisture travelled a greater
distance and had multiple fractionations before the rain-
fall event (Kendall and Doctor 2011). On the basis of
this distinct behaviour of the weighted monthly mean,
the groundwater data were plotted on the same graph
to determine the probable months of recharge (Fig. 6a
and for clarity Fig. 6b). The results showed that, March,
June and August contribute significantly to groundwater
13
 Sustain. Water Resour. Manag.

recharge while the evaporated groundwater receives sig-

DE discharge elevation, EC electrical conductivity, R(Cl) recharge estimate using CMB, RCl(%P) recharge as percentage of precipitation, R(18O) recharge estimate using δ18O shift method,
760.92
757.08
724.00
731.51
738.17
753.39
787.27
788.62
724.00
788.61
755.12
nificant recharge from February rains.
AR
m
The high groundwater recharge estimated from the CMB
and the δ18O shift method suggests high fortunes in terms
R18O(%P)

of commercial groundwater resources development in the

14.18
69.73
83.10

83.10
25.06
area, if a significant proportion of it is available for abstrac-
9.92
8.33
2.83
3.45
8.92

2.83
%

tion. The wide range in the estimated data from the two
methods suggests significant spatial variation in ground-
R (18O)

119.01
100.00

107.02
170.13
836.70
997.23

997.23
300.68
33.93
41.41

33.93
water recharge rates in the study area. This apparent high
mm

variability in direct groundwater recharge from rainfall in

the area was found to be a characteristic of the Voltaian
RCl(%P)

basin due to the variation of the clay content in space in

22.38

10.53

35.81
44.76
65.39

65.39
26.46
7.79
5.12

19.9

5.12
the unsaturated zone (Oteng Mensah et al. 2014). Where
%

the clay content is considerably high, vertical percolation

of rainwater is much reduced, leading to reduced vertical
268.58

126.39
238.74
429.73
537.17
784.63

784.63
317.51
R(Cl)

93.42
61.39

61.39

recharge. Infiltrating rainwater experiencing such restricted

mm

vertical flow, therefore, undergoes significant evaporation

such that a high percentage is lost to the atmosphere. The
16.00
45.99
69.98
33.99
17.99
10.00

69.98
25.93
mg/l

8.00
5.48
5.48

spring water shows a comparatively higher recharge esti-

Cl

mates by both methods. Based on the altitude of recharge

and discharge of the springs, the spring water flow system
‰VSMOW

are mainly local and to some extent intermediate.

−14.68
−13.90
−10.06
−10.08
−11.60
−10.25
−11.14
−10.18
−14.68
−10.06
−11.47

Groundwater in this region is a perennial source of

H

water supply for the growing population. Despite the high

2

estimated groundwater recharge and the high potential for

‰VSMOW

groundwater utilization in the area, there are no records on

groundwater table fluctuations and piezometric heads. For
−2.90
−2.85
−2.42
−2.52
−2.87
−2.99
−3.24
−3.26
−3.26
−2.42
−2.88
Table 5  Results of the physico-chemical, recharge and altitudes of recharge of the spring water

a sustainable exploitation of groundwater in the area, there

O
18

is a need for an assessment of the renewal rate which will

guide the rate of abstractions of this valuable resource.
312.00
554.00
348.00
117.90

554.00
198.19
us/cm

92.90

58.10
50.30
52.30
50.30
EC

Conclusion
203
692
692
697
688
714
734
519
203
734
617
DE

R18O(%P) recharge as percentage of precipitation, AR altitude of recharge

m

The present study investigated the groundwater and spring

0.3520
0.4381
0.4373
0.4371
0.4340
0.4405
0.4353
0.4259

water dynamics, origin and recharge mechanisms based

East

on a systematic sampling and analysis of δ2H and δ18O in

rainwater, groundwater and spring water in the Amedzofe
6.74160
6.84872
6.84884
6.84896
6.84588
6.84351
6.84162
6.82554

area. The rainwater stable isotopes based on the individual

North

rainfall events gave a local Meteoric Water Line (LMWL)

of δ2H = 7.32 δ18O + 8.20 (n = 113; r2 = 0.94). A further
development of LMWL for heavy rainfall events greater
Sample id

than 10, 20 and 30 mm and using the amount weighted

AMS2
AMS1
AMS3
AMS4
AMS5
AMS6
AGS

AVS

mean orient the slope closer to the Global Meteoric Water

Line (GMWL). The results also showed that, rainwater sta-
ble isotopes are mainly influenced by the rainfall amount
AVATIME VANE SPRING

with temperature having minimal effect. All the spring

AMEDZOFE SPRING
AMEDZOFE SPRING
AMEDZOFE SPRING
AMEDZOFE SPRING
AMEDZOFE SPRING
AMEDZOFE SPRING

water and most of the groundwater are of meteoric ori-

gin with some groundwater showing evidence of isotopic
Sample location

AGR SPRINGS

enrichment due to evaporation. The Chloride Mass Balance

(CMB) and δ18O shift methods gave mean groundwater
recharge of 10.70 and 8.39% of annual rainfall, respec-
Mean
Units

Max
Min

tively. The CMB estimated mean spring water recharge

13
Sustain. Water Resour. Manag.
Fig. 8  Estimated recharge -2.1
elevation of the springs in the -2.2
study area
-2.3
-2.4
-2.5
-2.6
δ 18O (‰)
-2.7
-2.8
-2.9
-3
-3.1
-3.2
-3.3
-3.4
-3.5
700
of 26.46% while the δ18O shift method gave a recharge
of 25.06%. From the stable isotopes data of rainfall from
Kpando and Amedzofe, the estimated altitude effect was
0.17/100 m while altitudes of recharge of the springs range
from +724.00 to +788.61 m amsl. Two distinct moisture
sources were identified, namely, evaporated surface water
bodies and evapo-transpiration water vapour flux from veg-
etation (isotopically enriched local moisture) and Atlantic
Ocean (isotopically depleted moisture source). The results
further showed that significant groundwater recharge in the
study area takes place in the months of March, June and
August.
Acknowledgements The data presented are part of an ongoing sam-
pling of the Global Network of Isotopes in precipitation (GNIP) sup-
ported by the International Atomic Energy agency. The research was
also partly funded by the International Foundation of Science (IFS)
with Grant No. AI2W/31196 for setting up a modern weather station.
The authors wish to express our profound gratitude for this support.
We are also grateful to Mr. Attah Biribi of Amedzofe meterological
station for his assistance in sampling. Special thanks go to the anony-
mous reviewers and the editors for their critical reviews and helpful
comments.
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