APPROVAL SHEET

ETHIOPIAN INSTITUTE OF WATER RESOURCES

ADDIS ABABA UNIVERSITY
SCHOOL OF GRADUATE STUDIES

Geochemical and Numerical Modeling of Groundwater Flow

Dynamics and Solute Transport in Tectonically Active Rift
Systems: the Case of Lower Awash Basin, Ethiopia
Submitted By:

Engdasew Temere Taye _________________ ______________

Name of Student Signature Date

Approved By:

Dr.Abdelwassie Hussien _______________ ______________

Major Advisor Signature Date

Dr. Taye Alemayehu___ _______________ ______________

Co-Advisor Signature Date

Dr. Neil Burnside _______________ ______________

Co-Advisor Signature Date

Dr. Zeleke Agide___ _______________ ______________

External examiner Signature Date
Bayou Chane ________________ _______________
Internal examiner Signature Date
________________ _______________ ________________
Chairman, DGC/SGC Signature Date
_____________ _____________ _____________

Dean, SGS Signature Date

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 Geochemical and Numerical Modeling of Groundwater Flow
Dynamics and Solute Transport in Tectonically Active Rift
Systems: the Case of Lower Awash Basin, Ethiopia
By: Engdasew Temere

Department: Water Resources Engineering and Management

(Specialization in Groundwater Management)

Main Advisor: Abdelwassie Hussien (Associate Professor, Mekelle University)

Co-Advisor: Taye Alemayehu (PhD, Assistant Professor, AAU)
: Neil Burnside (PhD, Assistant Professor, University of Strathclyde)

September, 2021

Addis Ababa, Ethiopia

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 Table of contents
INTRODUCTION .......................................................................................................................... 7
1.1. Background to the study .................................................................................................................... 7
1.3. Research Questions .......................................................................................................................... 10
1.4.1 General Objective ...................................................................................................................... 10
1.4.2 Specific Objectives..................................................................................................................... 11
1.5. Scope of the Study ........................................................................................................................... 11
1.6. Significance of the Study ................................................................................................................. 11
2. LITERATURE REVIEW ......................................................................................................... 12
2.1. Determining the area and mechanism of recharge and discharge condition of the groundwater ... 12
2.1.1. Mechanism of Recharge............................................................................................................ 12
2.1.2. Ground Water Discharge Condition.......................................................................................... 13
2.1.3. Assessing surface water groundwater interaction ..................................................................... 14
2.2 Determining the sources and age of groundwater ............................................................................. 16
2.2.1. Sources of groundwater ............................................................................................................ 16
2.2.2. Age of the groundwater............................................................................................................. 17
2.3. Hydrochemical evolution, major geochemical processes, and water quality of groundwater ......... 17
2.4. Developing groundwater flow and solute transport model .............................................................. 20
2.4.1. Ground Water Flow Modeling .................................................................................................. 20
2.4.2. Solute Transport Flow Modeling .............................................................................................. 21
3. Description of the study area .................................................................................................... 25
3.1. Location of the Study Area .............................................................................................................. 25
................................................................................................................................................................ 25
3.2. Climate ............................................................................................................................................. 25
3.3. Geology ............................................................................................................................................ 26
3.4. Structure ........................................................................................................................................... 26
3.5. Hydrogeology .................................................................................................................................. 28
4. MATERIALS AND METHODS.............................................................................................. 30
4.1 Data collection, Sampling and In-situ measurements ....................................................................... 30
4.1.1 Data collection ........................................................................................................................... 30
4.1.2. Sampling and In-situ measurements ......................................................................................... 30
4.2. Analytical techniques ....................................................................................................................... 31

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 4.2.1. Stable Isotopes .......................................................................................................................... 31
4.2.3. Radon (Rn-222) ........................................................................................................................ 32
4.2.4 Radioactive Carbon (14C) ........................................................................................................... 32
4.2.5. Hydrochemistry ......................................................................................................................... 32
4.3. Determining the mechanism of recharge and discharge .................................................................. 34
4.3.1. Mechanism of recharge ............................................................................................................. 34
4.3.1.1. Stable isotope ..................................................................................................................... 34
4.3.2. Discharge condition .................................................................................................................. 35
4.3.2.1. Radon (222 Rn) .................................................................................................................... 35
4.3.3. Assessing surface water groundwater interaction ..................................................................... 35
4.3.3.1. Hydrochemistry.................................................................................................................. 35
4.3.3.2. Isotope (deuterium, oxygen-18) ......................................................................................... 36
4.3.3.3. Radon (222Rn) Isotope ........................................................................................................ 36
4.4. Determining the sources and age of groundwater .......................................................................... 36
4.4.1. Sources of groundwater ............................................................................................................ 36
4.4.1. 1. Stable isotopes................................................................................................................... 36
4.4.2. Age of groundwater .................................................................................................................. 37
4.4.2.1. Radioactive Carbon ............................................................................................................ 37
4.5. Characterizing the hydrochemical evolution and major geochemical processes ............................ 38
4.5.1. Hierarchical Cluster Analysis (HCA) ....................................................................................... 39
4.5.2. Principal Component Analysis (PCA) ...................................................................................... 39
4.5.3. Inverse Geochemical Modeling ................................................................................................ 40
4.5.4. Water Quality Index (WQI) ...................................................................................................... 41
4.6. Develop flow and transport modeling .............................................................................................. 42
4.6.1. Ground Water Flow Model ........................................................................................................... 42
4.6.1.1. Model Conceptualization and Input Data .......................................................................... 42
4.6.1.2. Model setup and running.................................................................................................... 43
4.6.1.3. Model Calibration .............................................................................................................. 44
4.6.1.3.1. Steady State Calibration ........................................................................................... 45
4.6.1.3.2. Transient State Calibration...................................................................................... 45
4.6.1.4. Verification and Validation ................................................................................................ 45
4.6.2. Transport flow model ................................................................................................................ 46

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 4.6.2.1. MT3D Model setup and running ........................................................................................ 46
4.6.2.2. Calibration.......................................................................................................................... 47
4.6.2.3. Model prediction ................................................................................................................ 47
5. RESEARCH SCHEDULE ........................................................................................................ 49
6. BUDGET .................................................................................................................................. 50
7. REFERENCES ......................................................................................................................... 51

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 Table of Figures

Figure 3. 1 : Location Map of the study area (Source, MWIR).................................................................... 25

Figure 3.2 : Geological and structural map of study area ( source , MWIR) ............................................... 27
Figure 3.3: Hydrogeological map of the study area ( Source, MWIR) ........................................................ 29
Figure 4.1: Schematic diagram of recharge-discharge condition of groundwater ..................................... 38
Figure 4.2: Schematic diagram of hydrogeochemical evolution and processes ......................................... 42
Figure 4.3: Schematic :Diagram of flow and transport modeling ............................................................... 48

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 INTRODUCTION

1.1. Background to the study

Water plays a key role in social and economic development around the world. Water resources
are commonly referred to as the surface water from rivers, lakes, streams, and subsurface water
from groundwater. Groundwater is usually reserved for the subsurface water that occurs beneath
the water table in soils and geologic formations that are fully saturated(Freeze & Cherry, 1979)

Water from beneath the ground has been exploited for domestic use, livestock and irrigation
since the earliest times Groundwater is easily the most important component and constitutes
about two thirds of the freshwater resources of the world and, if the polar ice caps and glaciers
are not considered, groundwater accounts for nearly all usable freshwater. The dominant role of
groundwater resources is clear and their use and protection is, therefore, of fundamental
importance to human life and economic activity. (Chapman, 1996)

The Ethiopian landmass consists of a large, high elevated plateau bisected by the Rift Valley into
the northwestern and the southeastern highlands, each with associated. The Ethiopian Rift
consists of three main sections: (i) the southern portion, from the border with Kenya to the
hydrological divide between Abaya and Awasa Lake; (ii) the main portion, commonly indicated
also as the Great Lakes Region of Ethiopia, stretching as far as the Awash River; (iii) the
northern portion, from the Awash to the apex of the Afar triangle and its northeastern branch, the
Danakil depression (Billi, 2015)

Ethiopia has a generous endowment of water, but this water is distributed unevenly in space and
time. Unmitigated hydrological variability, compounded by climate change, has been estimated
to cost the country roughly one-third of its growth potential (Mosello et al., 2015). Ethiopia
constitutes 99.3% of land area and the remaining 0.7% is covered with water bodies (MoWE,
2013).The country has 12 major basins, 12 large lakes, and differently sized water bodies. The
country’s surface water potential as identified and estimated in different integrated river basin
master plans is 124.4 billion cubic meter (BCM). ((Berhanu et al., 2014)
The occurrence of groundwater is mainly influenced by the geophysical and climatic conditions
of the area. The difficulty in obtaining productive aquifers is a peculiar feature of Ethiopia,
which is characterized by the wide heterogeneity of geology, topography, and environmental

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conditions ( Alemayehu, 2006).In many parts of the country, groundwater is an important source
of domestic and industrial water use especially in rural areas and towns. With the understanding
of the nature of the distribution of these rocks and the recharge classification of the country, (
Alemayehu, 2006), estimated the total groundwater reserve of the country as 185 BCM, which is
distributed in an area of 924,140 km2 made of Sedimentary, Volcanic, and Quaternary rocks and
sediments, including the highlands and the Rift Valley

The Awash basin receives 100 – 1700mm mean annual rainfall with its wide spatial and
temporal variation. According to the annual water balance the basin generate 10.3BCM water for
ground water recharge, 4.6BCM water as stream flow, and 3.6BCM water as stored in open
water systems that include lakes, reservoirs and wetlands of the basin. Therefore the water
potential of the basin can be accounted as 8.2BCM surface water and 10.3BCM ground water
potential with 300m exploration. In the Awash terminal river water potential is 1.19BCM and
groundwater 0.07 BCM and the water demand system of the irrigation 1057 MCM (ARBA, 2017).

In much of the arid and semi-arid areas in which surface water is scared like in lower awash
basin, in which frequently affected by drought. The people living in the study area mainly
dependent on animal pastoralists’ .So the local communities depend mainly on groundwater but
water quality aspect of the ground water is also crucial problem in the area.

The characteristics of groundwater chemistry are primarily influenced by recharge water

chemistry, water-rock interactions, solute transport, and chemical processes occurring along the
flow paths (André et al., 2005). Hydrogeochemistry and isotope hydrology can be used for the

interpretation of the type and origin of groundwater recharge, to decipher reactive processes, and
calibration of hydrological models. Additionally, hydrogeochemical and isotopic data are useful
for identifying sources of recharge and groundwater flow(Glynn & Plummer, 2005). Isotope and
hydro-chemical methods are some of the approaches to investigate the interaction between
surface water and groundwater study. The isotope methods additional give the insight to detect
the origin of water, groundwater inflow zones, and rates of groundwater (Ayenew, Demlie, and
Wohnlich, 2008a; Kebede and Zewdu, 2019). Within the study area, some researchers have
conducted studies on groundwater flow and solute modeling using hydrogeochemistry, isotope
and MODFLOW/MTD3

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MT3DMS is widely modular 3D model to simulate solute transport in porous medium in porous
medium which is based on the solution of groundwater from MODFOW simulation( Zheng &
Wang, 1999). In an interest of in analysis of ground-water flow and contaminant movement
systems, MODFLOW can simulate a wide variety of hydrological (USGS, 1997)

The main objective of this study is to modeling groundwater flow and solute transport of lower
awash of through integrated analysis of hydrochemical, isotopic data and modeling. The results
will contribute to generate scientific information for the local hydrogeology and be supportive
for the sustainable management of the groundwater in this multilayered aquifer system

1.2. Statements of the problems

The hydrogeological functioning and aquifer system of the Ethiopian rift valley are generally
complex compared to other aquifer systems located outside of this rift system (Mechal et al.,
2017). This is mainly due to the occurrence of groundwater in complex rift volcanic products
highly controlled by geological structures. The success rate of productive wells in the arid
lowlands of Ethiopia is still very low (30-50 per cent), even by sub-Saharan African standards.
The key problem contributing to this low rate of successful boreholes is attributed to the lack of
adequate scientific information and surface/subsurface investigations pertinent to the
hydrogeological (Ketema et al., 2016).
The area is dominated by arid-climatic condition and frequently affected by drought. The main
surface water flow in the area is Awash River Thus; groundwater becomes the sole dependable
resource of sustainable development and domestic water supply. A number of hand dug wells are
kept on digging to fulfill the demand of the water supply. The very shallow wells have quality
issues. Since the groundwater levels of the boreholes are near to the surface, human induced
pollution as well flood caused by rainfall events can readily pollute these groundwater wells.
According to (Mekonnen et al., 2015) , Water samples, which had a high concentration of nitrate,
were collected from Dubty, Assaita, , Eldar, Afambo, Hamiltole, Handeg, Geyreni, and Gilifega
village in which these villages are located in the lower valley of the Awash River .In the area
groundwater affected by geothermal water have high salinity(Gizaw, 1996).

Most research in awash basin focused on the upper and middle part of the basin .Even if there
are researches in lower awash regarding hydrogeological investigation, there is no research on

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modeling of groundwater flow and solute transport using the methods of hydrogeochemistry,
isotope and modeling through MODFLOW/MTD3. Therefore these and other related problems
needs some further and detail investigations to indicate some possible ways and mechanisms for
sustainable, potable and feasible water resource development programs in the area. The study in
general focus and incorporates the evaluation of the hydrochemistry, ground water flow
dynamics, Interaction of groundwater with surface water, recharge- discharge condition and
possible flow directions of solutes which would have a direct contribution for water quality. The
combined interpretation of groundwater chemistry environmental isotopes, flow and transport
modeling can help to modeling groundwater flow dynamics and solute transport particularly in
complex hydrogeological system of the area which are important for sustainable water resources.

1.3. Research Questions

1. Where is recharged area of the groundwater and what is the mechanism condition of recharge
and discharge?
2. What is the source and age of the recharged groundwater?

3. How does the groundwater chemistry evolve, major geochemical processes, and water quality
of groundwater along the flow path in the different rock units and geological structures?

4. How can groundwater flow model improve our understanding on groundwater flow and solute
transport in the study area?

1.4. Objectives of the Study

1.4.1 General Objective

The general objective of this research is modeling of groundwater flow dynamics, solute
transport and surface water -groundwater interaction lower awash basin.

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1.4.2 Specific Objectives
 To determine the area and mechanism of recharge and discharge condition of the
groundwater system.
 To determine the sources and age of the groundwater
 To characterize the hydrochemical evolution, major geochemical processes, and water
quality of groundwater along the flow path in the different rock units and structures
 To develop a groundwater flow and solute transport model

1.5. Scope of the Study

The research aim is to model the groundwater flow dynamics, solute transport and groundwater –
surface water interaction in lower awash basin specifically terminal part of the basin using
hydrogeochemistry, isotope and Groundwater flow and transport modeling
(MODFLOW/MT3D).The (MODFLOW/MT3D). Will use to model the ground water flow
dynamics and solute transport .The methods will not intend to provide all aspects of ground
water system studies due to lack of data. Even the available data are not systematically organized
and studies in the area are not in detail extent. The methods that will apply is use to identify
problems like recharge sources and mechanisms , discharge condition , ages of ground water ,
groundwater quality , major geochemical process , hydrochemical evolution , flow dynamics
and contaminate transport .

1.6. Significance of the Study

The study significantly contributes to the understanding of the groundwater flow dynamics,
solute transport, hydrogeochemical evolution, and water quality of the area which is very
important for sustainable management. Currently, the government has been paying much
attention for water resource development in such arid areas and this research is in line with such
a program will have extensive practical use for future development of water resources. The new
data generated in the research will also enable further research at a larger scale in the area.

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 2. LITERATURE REVIEW
2.1. Determining the area and mechanism of recharge and discharge condition of
the groundwater system

2.1.1. Mechanism of Recharge

Recharge relates to the water added to the groundwater system, that is, to the saturated zone.
Thus, the recharge is the balance between the amount of water that infiltrates into the ground and
evapotranspiration losses in which the recharge region has low Salt content (B. Misstear, 2000).
The factors that influence the amount and type of recharge (diffuse or focused) include
precipitation; vegetation and evapotranspiration; soil and subsoil types; flow mechanisms in the
unsaturated zone); bedrock geology; available groundwater storage and the presence of influent
rivers, (B. D. R. Misstear, 2000)

Recharge to aquifers takes place in a variety of mechanisms including direct diffuse recharge and
Indirect recharge from floodwaters during high flood stage, mountain block and mountain front
recharge, fast selective recharge from heavy rains and recharge from losing streams and flash
floods and more than ¾ of aquifers in Ethiopia receive localized and indirect recharge as the
dominant mechanisms for recharge (Seifu, 2012).

According to (Wilson & Guan, 2013), Mountain-front and mountain-block recharge defined as
water entering adjacent inter-mountain basin-fill aquifers, with its source in the mountain front or
mountain blocks that describe the important role for many aquifer systems in arid or semi-arid
areas of the contribution from mountains to the recharge of aquifers in adjacent basins.Most
areas at the interface between the Ethiopian rift and adjacent mountains get their recharge from
mountain front-mountain block recharge (Seifu, 2012).

The study by (Wang et al., 2013) with the purpose of understanding sources and mechanisms of
groundwater recharge in the Ejina Basin in which the result indicate an arid inland river basin in
northwest China based on the stable isotope levels (d18O and d2H) of the surface water and the
shallow phreatic groundwater, river infiltration and desert front recharge should be considered as
the two main recharge mechanisms of the Ejina aquifer.

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(WMO, 2012)): Generally, groundwater in recharge areas and shallow aquifers where contact
times are of the order of years or decades is lower in total dissolved solids than groundwater in
transit and discharge areas and deeper aquifers where residence time maybe centuries and flow
velocities very low.

(Saka et al., 2013)was performed to assess groundwater in the Ga West Municipal Area of
Ghana using hydrogeochemistry and isotope approaches and conclude that from the oxygen and
hydrogen isotope compositions in the groundwater samples; groundwater recharge is of meteoric
origin with few samples showing evidence of evaporation. An average deuterium excess of
rainfall of 14.2 % was observed, which indicates the significance of kinetic evaporation due to
low humidity conditions prevalent in the study area. The d-excess also indicates modern recharge
along the foothills of the Akwapim Togo Ranges.

2.1.2. Ground Water Discharge Condition

Discharge relates to the emergence of groundwater at the surface as springs, water feeding
swamps, and lakes, and water pumped from wells in which discharge areas characterize in Water
table levels mark, in most cases, a high in the water table contour map (Mazor, 2004). A
discharge is the portion of the drainage basin in which the net saturated flow of groundwater is
directed toward the water table(Freeze & Cherry, 1979).

Groundwater discharge may represent a threat to surface water quality, ecosystem health, and
the related ecosystem service provision due to the potential transport of excessive nutrient loads,
heavy metals, or organic pollutants (e.g., (Rodellas et al., 2015; Rocha et al., 2016).

On a global scale, groundwater discharge is expected to be responsible for 5-10 % of the

freshwater input to the oceans (Burnett & Dulaiova, 2003); (Igor S Zektser et al., 2006)), but
roughly for one-third of the global input of dissolved solids (I S Zektser & Loaiciga, 1993).

222
Over the past few years, several studies used natural radium isotopes and Rn to assess
groundwater discharge into the ocean (Corbett et al., 1996)(Ellins et al., 1990). Hence, the
quantitative understanding of groundwater discharge processes is a prerequisite for integrated
water resource management.

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(Cook et al., 2004): applied radon activities within surface waters and the total estimated
groundwater discharge to surface waters is 30 000 – 150 000 ML/yr., and the majority of the
discharge to surface waters occurs to the Burdekin River, Haughton River, Barratta Creek, and
Plantation Creek.) The groundwater discharge directly into Bowling Green Bay is estimated to
be 50 – 400 000 ML/yr.

(Petermann et al., 2018) reported that steady-state annual isotope mass balances for both δ18O
and δ2H are consistent and reveal an overall long-term average groundwater discharge that
ranges from2, 800 to 3,350 m³ d-1. These findings were supported by the good agreement of the
simulated annual cycles of δ18O and δ2H lake inventories utilizing the determined groundwater
discharge rates with the observed lake isotope inventories. However, groundwater discharge
rates derived from radon mass balances were significantly lower, which might indicate a distinct
seasonal variability of the groundwater discharge rate.

(Tilahun, 2015): presented that the highest reading, 600 to 800 Bq/m3 of 222Rn activity was from
the downstream part of the Awash River where the geologic unit is dominated by rift basalts and
ignimbrites and lineament density is high. This zone is identified as a discharge zone for the
regional groundwater into the Awash River flow system. From the highest values in this zone, it
can be concluded that the groundwater that discharges into the Awash River flow system in areas
at its outlet has a relatively long residence time flow path length.

2.1.3. Assessing surface water groundwater interaction

The groundwater-surface water interactions are pretty common in large inland basins, playing a
necessary role in maintaining the ecosystem of river (Kalbus et al., 2006)). It is crucial to
understand the relationship between groundwater and surface water for sustainable utilization
and management of precious water resources, especially in the arid and semi-arid areas.

Two main, basic situations of hydrologic exchange between surface water and groundwater are
recognized: (a) an effluent condition, where subsurface water drains into the stream, also known
as gaining stream, and (b), an influent condition, where surface water contributes to groundwater
flow, also known as losing stream (Bailly-Comte et al., 2009, Brunner et al., 2011.,Dor et al.,
201)). However, the behavior of any given surface water–groundwater system is not static but

14
dynamic (Bailly-Comte et al., 2009), as a river could be receiving groundwater in some sections
and losing water to groundwater in others (Kalbus et al., 2006,Newman et al., 2006).

(Tenalem &Nardose, 2008)): A steady-state groundwater flow model (MODFLOW) was used to
study lake and groundwater interactions in a complex rift volcanic catchment. The model
simulations were made after first developing a reasonable conceptual model, based on
conventional hydrogeological mapping, pumping test and hydro-meteorological data analyses,
and from ancillary information obtained from Hydrochemical and isotope techniques. The model
results indicated that the lakes and Rift aquifers are fed by large groundwater inputs that
originate in the highlands.

(Martinez, 2017): A spatial analysis of hydrochemical data of groundwater and surface water
was undertaken to identify groundwater-surface water connectivity in the headwaters of the
Conda mine River catchment, Southeast Queensland, Australia.. The proportion of groundwater
222
contribution to stream flow calculated by Rn and chloride mass balance is in agreement and
ranges between 20-70% in tributaries in the northern areas, and between 8-50% in the upper
reaches of the main river channel.

(Wang et al., 2013): In this study, multi environmental tracers (Hydrochemical parameters, stable
222
hydrogen, and oxygen isotopes, and radioactive Rn) were employed to investigate the
interaction between groundwater and surface water along two rivers (Tiangeli River and
Nomhon River) in the Nomhon area, southeast of the arid Qaidam Basin, northwest China. The
stable isotopic compositions (δD and δ18O) and Hydrochemical characteristics (Hydrochemical
type, TDS, and EC) showed corresponding changes along these two rivers, which also provided
evidence for the groundwater-surface water interactions in the Nomhon area.

(Tsedenya, 2018): performed research with the objective of Groundwater-Surface water

interaction along the main course of Awash River through multiple methods, a namely stable
isotope of water (2H and 18O), an isotope of Radon (222Rn), piezometer evidence as well as field
Physico-chemical characteristics. The result Showed that deep groundwater in the middle and
Lower Awash can be considered as separate water resources, whereas, deep groundwater in
Upper Awash are hydraulically connected to Awash River.

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(Taye et al., 2017): Did the research based on the Analysis of radon-222 that shows no
significant groundwater flux over the wetlands, which are part of Machar Marshes. This shows
evaporation to be the dominant hydrologic process in this zone.

2.2 Determining the sources and age of groundwater

2.2.1. Sources of groundwater

Recharge derived from rainfall can occur via direct or indirect means .Direct recharge is
rainwater that percolates where it falls straight into the soil zone, whereas indirect recharge takes
place from rainwater that is transported overland, for example, as runoff via Wadis with
secondary infiltration to the vadose zone. In semi-arid and arid regions, indirect recharge is an
important mechanism (Wheater & Al Weshah, 2002)

(Tilahun , 2015): carried out a study on recharge mechanism based on δ18O and δD signature
from shallow aquifer systems in all the sub-basins suggest that the aquifer system is locally
recharged from modern precipitations and the radioactive age show that recharges to the aquifer
systems is dominated by modern waters.

(Oiro et al., 2018): conducted research, to investigate probable recharge scenarios by the spatial
isotope maps and the result showed three probable recharge scenarios: (1) preferential/ direct
recharge in the north and west facilitated by faults, permeable volcanic soil, and high rainfall
inputs, with an altitudinal depleted isotope signature; (2) delayed induced recharge in the central
part of the aquifer from impounded lakes and wetlands, with enriched isotope signatures; and (3)
focused groundwater recharge in the south and east associated with flooding in floodplains

Indirect recharge from floodwaters and depression storage is the most common recharge
mechanism and accounts for more than 20 % of recharge taking place in Ethiopia. Floods leading
to recharge can emerge from the area where recharge is taking place or can originate from
highlands bounding the arid lowlands. There is clear evidence for this type of recharge in
dominating recharge mechanism in Afar depression (Tenalem et al., 2008).

(Lu et al., 2015): showed intending to identify the sources and recharge mechanisms of the
groundwater by an analysis of the stable isotopes and the major ions in the surface water and

16
groundwater in the Leizhou Peninsula. The regression equations for 𝛿D and 𝛿18O for the surface
water and the groundwater are similar to those for precipitation, indicating meteoric origins.

2.2.2. Age of the groundwater

Knowledge of groundwater residence time is very useful in understanding groundwater

dynamics in aquifers. However, the interpretation of 14C activity in terms of groundwater age is
not simple. Indeed many studies have demonstrated that it is impossible to estimate groundwater
age without access to other isotopic or chemical indicators in addition to 14C activity ((Glynn &
Plummer, 2005)Clark & Fritz, 1997)..

The isotopes of water and the ages of water (based on isotopes) may provide a more regional
understanding because there is less potential rock-water interaction on an aquifer by aquifer
basis(Kreitler et al., 2013).Investigating the residence time of groundwater (i.e. the period from
recharge to drainage in pumping wells, springs, or streams) reveals information about water
storage, mixing, and transport in subsurface water systems (Cartwright et al., 2017; de Dreuzy &
Ginn, 2016; McGuire & McDonnell, 2006).

The detailed analysis of the results in the Triassic aquifer, including the radiocarbon age
corrections and the comparison of radioisotope activities, has made it possible to estimate the
range of residence time within the carbonate Triassic aquifer. This range from several tens to
several tens of thousands indicates that the recharge of aquifers might have occurred between
modern times and the Pleistocene.(Samborska et al., 2013)

(Taye et al., 2017): research-based on Analysis of the oxygen, deuterium, and tritium isotopes
show the groundwater of the Baro-Akobo Basin is modern water.

2.3. Hydrochemical evolution, major geochemical processes, and water quality of

groundwater

Geochemical reactions along ground-water flow paths can lead to regional variations in water
composition that evolve in the direction of flow. In more complex cases, the concentration of
reactive constituents may vary spatially and temporally along the recharge area, and may also
evolve along the direction of flow. Recent studies show that the composition of groundwater

17
hydrochemical can help define groundwater flow patterns in the aquifers (Coetsiers &
Walraevens, 2006).This information is very important in groundwater systems, especially those
consisting of multilayer aquifers.
The motion of groundwater along its flow paths increases the concentration of the chemical
species. This depends on the geological formation, geological structure and is determined by the
interaction processes between the water and hosting rock (Domenico & Schwartz, 1998; Freeze
& Cherry, 1979; Kortatsi, 2007; Aghazadeh & Mogaddam, 2010). The assessment of
Hydrochemical changes along groundwater flow paths highlights how aquifers are separated in
some areas and how mixing between groundwater from different aquifers occurs elsewhere
controlled by geological structures, sedimentary (Moya, 2015).

In a hydrothermal system, the mixing process has specific implications for the geothermometry
and for assessing the hydrogeology of the spring system and the geothermal reservoir. Fractured
rock aquifers are the dominant groundwater systems in geothermal regions (Clayton & Steiner,
1975). Recent studies indicate that groundwater associated with fractured bedrock aquifers show
consistent chemical and isotopic variations between the shallow recharge zone, the shallow
fractured zone, and the deep fractured system (Cook et al., 2005;L ;Laaksoharju et al., 2008,
Afsin et al., 2014)

There is a general zonation of salinity with altitude. As the altitude decreases the salinity
increases. Highland waters are of low salinity. In the rift floor deep aquifers the salinity and ionic
concentration are high (Tenalem, 2005)). This variation was interpreted in terms of groundwater
chemical evolution along the groundwater flow paths. In several localities, large pockets of
anomalously saline groundwater were observed suggesting the lack of continuity in the
groundwater flow or in terms of mixing with deep thermal waters (Seifu et al., 2008).

In the Afar, the high groundwater salinity is attributed to the leaching of evaporite and lacustrine
deposits (Tenalem, 2005).In the basic highland volcanic calcium (Ca) and magnesium (Mg) are
the dominant cations that form hard waters. In the rift where acidic volcanic are common sodium
(Na) becomes more important.

18
(Bretzler et al. (2011): The study aims to investigate groundwater recharge and flow patterns in
tectonically active rift systems, exemplified by a case study in the Main Ethiopian Rift. The
chosen approach includes the investigation of Hydrochemical parameters and environmental
isotopes (3H, d2H, d18O, d13C-DIC, 14C-DIC, 87Sr/86Sr). Hydrochemical and isotopic data indicate
an evolutionary trend existing from the escarpments towards the Rift floor. Groundwater evolves
from tritium-containing and hence recently recharged Ca–HCO3-type water on the escarpments
to tritium-free Na–HCO3 groundwater dominating deep Rift floor aquifer.

(Abrham Asha &Tenalem Ayenew, 2019): There is strong spatial hydrochemical variation
between the rift and highlands in identifying four major groups of water types evolving from Ca-
HCO3 at highlands to Na-Cl highly evolved thermal water. The four groups have ten subgroups
indicating clear geo-hydrological patterns along the groundwater flow path representing different
lithology, residence time, degrees of rock–water interaction, and aquifer composition.

(El Alfy et al., 2017): In this study, integration of Hydrochemical investigations involving
chemical and statistical analyses are conducted to assess the factors controlling hydrochemistry
and potential pollution in an arid region. These factors indicated that the chemical characteristics
of the groundwater were influenced by rock water interactions and anthropogenic factors. The
geogenic factors include the dissolution of various minerals (calcite, aragonite, gypsum,
anhydrite, halite, and fluorite) and ion exchange processes. The anthropogenic factors include the
impact of irrigation return flows and the application of potassium, nitrate, and phosphate
fertilizers).
.
(Saka et al., 2013): This paper assesses groundwater in the Ga West Municipal Area of Ghana
using hydrogeochemistry and isotope approaches.The dominant groundwater composition in
both shallow and deep wells sampled is Na–Cl. The concentration of the Na–Cl was observed to
increase substantially with wells depths. The mixing of freshwater of the shallow hand-dug wells
with that of saline water of the deep boreholes was noted in the shift from Ca–HCO3 facies to
Ca–Cl.

19
2.4. Developing groundwater flow and solute transport model

2.4.1. Ground Water Flow Modeling

Modeling is a multi-phase process progressing through the broad stages from the definition of
modeling objectives, data review and conceptual modeling, to model setup (including disclosure
of key modeling assumptions) and calibration through to model predictions and uncertainty
analysis.. The uncertainty analysis of predictive models may indicate areas or data types that are
required to decrease uncertainty(Wels et al., 2012).

In the late 1960s, following the development of computers and digital technology, numerical
models were widely adapted to provide a more comprehensive vision of the groundwater
systems under complicated conditions. With numerical modeling, hydro geologists were directly
able to approximate the solutions of complicated differential equations of the system by
converting them to discrete equations and dissecting the domain into meshes or grid (Saatsaz &
Eslamian, 2020)

The process of groundwater flow is generally assumed to be governed by the relations expressed
in Darcy's law and the conservation of mass. The finite difference methods are perhaps the best
known among the numerical techniques used to solve a set of partial differential equations based
on the geometry of the system, boundary conditions, and initial condition. (Saatsaz & Eslamian,
2020). The partial differential equation of groundwater flow used in mod flow

( ) ( ) ( ) Q S

e kx and Kz are values of hydraulic conductivity along the x, y, and z coordinate axes,
which are assumed to be parallel to the major axes of hydraulic conductivity (L/T), h is the
potentiometric head (L), Q is a volumetric flux per unit volume representing sources and/or sinks
of water, SS is the specific storage of the porous material (L-1), t is time.

The software programs for solving the mathematical models numerically can use by applying the
finite difference method. MODFLOW code is commercial software designed to describe and
predict the behavior of groundwater systems,(Chiang et al., 1998). This model employed Finite

20
Difference techniques to simulate the hydrodynamic of the groundwater flow under non-
equilibrium conditions in a heterogeneous and anisotropic medium.

Groundwater flow models have been routinely used to calculate the rate, velocity, and direction
of groundwater flow within and across the boundaries of an aquifer system (Mandle, 2002). The
outputs of a groundwater flow model are the hydraulic heads and groundwater fluxes that are in
equilibrium with the physical and hydrogeological conditions defined for the model.

2.4.2. Solute Transport Flow Modeling

A solute is a substance dissolved in a liquid. The transport of solutes in groundwater and surface
water is influenced by a variety of processes.. Physical processes are more dominant during the
transport of conservative or non-reactive solutes such as the chlorides and bromides. For reactive
solutes such as the nutrients N and P, other processes may be dominant (Appelo & Postma, 2004;
(Runkel et al., 1996).. There are three basic processes of transport of contaminant: Advection,
Molecular Diffusion and Mechanical Dispersion.

Advection is the movement of contaminants that occurs because they are being carried along
with the moving groundwater. Thus, when only advection is considered, a contaminant moves as
fast as groundwater and therefore there is no attenuation in the concentration of the solute
considered (Jemal Seid, 2009). The mass flux equation is therefore (Batu, 2005):

Where is mass of solute per unit cross sectional area transported in the x direction per
unit area.

𝒗𝒙 is the Darcy velocity in the same direction

𝝋𝒆 is effective porosity
𝑪 is the initial concentration of the solute
𝒒𝒔 is the groundwater velocity or pore water velocity

Molecular Diffusion is the movement of dissolved ions from regions of high concentration to
regions of low concentration which is represented by Fick’s law of diffusion which is modified

21
for saturated porous media and it occurs even when the fluid is at rest (Fried and Combarnous,
1971-as cited in Batu, 2005.

Where: 𝑑𝑖𝑓𝑓 is mass flux unit time per unit area

𝐷 is the effective molecular diffusion coefficient
𝜕𝐶/𝜕x is concentration gradient
is the distance
𝜑 is the effective porosity

Dispersion is mixing that occurs as the water containing a contaminant(s) flows around the solids
in the aquifer media.

Where: is mass flux per unit time per unit area and Dm is mechanical dispersion
coefficient

The software program; ‘‘MT3D'' applies for the determination of contaminant transport
movement and distribution. It communicates with the MODFLOW program through data files.
This will be linked to a known groundwater movement to determine the distribution and
movement of contaminants in groundwater.
The partial differential equation describing the three-dimensional transport of contaminants in
groundwater can be written as follows

(𝐷 ) C) 𝐶 ∑

Where: C: the concentration of contaminant dissolved in groundwater, t: time, xi: the distance
along the respective Cartesian co-ordinate axis, Dij: the hydrodynamic dispersion coefficient

22
 the seepage or linear pore water velocity, , the volumetric flux of water per unit volume
of aquifer representing sources (positive) and sinks (negative, 𝐶 the concentration of the sources
or the sinks, the porosity of the porous medium; and Rk: chemical reaction term

In flowing groundwater it is impossible to separate the processes of mechanical dispersion and

diffusion. The two are lumped together and treated as a single compound effect called
hydrodynamic dispersion. The effect of hydrodynamic dispersion is to cause a plume of
contamination to elongate in the direction of advection as well as to develop a gradient of
decreasing concentration from the center to the margins of the plume Sorption is a type of
surface reaction in which the solute is stuck to solid surfaces thereby delaying its arrival (L.
Elango, 2005).

(Abu-El-Sha’r & Hatamleh, 2007): In the study, five suggested scenarios of pumping with
different abstraction rates for years 2005 through2020 have been explored by using the three-
dimensional finite-difference flow model [MODFLOW (PM5)] to simulate the flow system, and
the solute transport model (MT3D) to predict the transport of total dissolved solids given in
terms of Electric Conductivity (EC.) The third scenario caused a slight increase in EC values
over the values simulated by other scenarios. Third, increasing the pumping rate by half Solute
transport by flowing water (dissolved suspended particles) has a broad impact on environmental
protection and resource utilization via groundwater contamination.

(Viraf Eruch, 1994) The study attempts to quantify and understand the effects of velocity and
flow path variations on the apparent longitudinal dispersion of a contaminant plume. A
numerical groundwater flow model of a high hydraulic conductivity aquifer was developed using
MODFLOW. The solute transport code MT3D was then used to model plume transport. Overall
the results of this study indicate that variations in groundwater flow direction and magnitude of
groundwater velocity within an unconfined aquifer system, cause an increase in the longitudinal
dispersivity of a slug injected contaminant plume. These flow field changes allow for large
portion of the solute to move transversely to the flow direction, causing more plume dispersion

23
The middle and lower parts of the Awash River basin are characterized by high
evapotranspiration, shallow saline water table and lack of natural drainage, and the irrigated
lands experienced with salinity, (Kidia Kessiee, 2019)

(IDOWU & NYADAWA, 2018): The direction of groundwater flow is predominantly towards
the north-eastern and southern parts of the study area. Finally, solute transport simulation shows
that concentrations of NaCl in the groundwater slightly reduced from the center of the study area
outwards from June (peak of rainy season) to September (post-monsoon).

(Saatsaz et al., 2013):2-D solute transport model for the aquifer has been developed, calibrated,
and validated using MT3D. The predictive simulation from October 2009 to October 2012 shows
that according to present recharge and discharge conditions, groundwater salinities will increase,
and in the mid and long-term, groundwater consumers will be facing a worse situation than the
present.

24
 3. Description of the study area

3.1. Location of the Study Area

The basin is found in central afar borders with Dankile basin and Republic of Djibouti which
comprises Asayita, Mile, and Dubti, Sirinka, Mersa and Hayk areas. The area can be sub-divided
into lower plan, lower valley and the western highland .The area contains fresh lake like lake
Ardibo and Hayk located near the edge of the northwestern rift escarpment and chain of lakes
of Gamari, Bario, Afambo, and Abe in the lower plane

Figure 3. 1 : Location Map of the study area

3.2. Climate

The Area is characterized by an arid and semi-arid climate with low and erratic rainfall. The
annual temperature and rainfall in the Asayita is 28-41.7°C and 144 mm annual precipitation,

25
respectively The climate in sub-humid rift escarpment is with average annual temperature and
rainfall of 18°C and 1158 (mm), respectively (Mola Demlie, 2000). Rainfall distribution is
mostly bimodal in the Lower Awash ash (Edossa et al., 2010)

3.3. Geology

During the Pleistocene pluvial period, very large lakes were formed on the floor of the Rift
Valley and the flat plains of Wonji, Metahara, and the Lower Awash Plains contain thick
successions of lacustrine deposits(Halcrow, 1989).

The geological formations of the Afar Depression and its marginal areas and surrounding
plateaus can be divided into four broad divisions like Pre-rift complexes, Syn-rift igneous rocks,
Pliocene–Pleistocene volcanic rocks Quaternary volcanic and sedimentary rocks and ((Beyene &
Abdelsalam, 2005; Bosworth et al., 2005)

Pre-rift stratified volcanic rocks along the rift margin and post-rift recent volcanic product and
basin filing sedimentary sequence in the rift floor mainly cover semera-Dubti area. Basalt is the
most common rock type that occurs as a broadsheet of flood basalts believed of fissural origin
and also younger flow from central volcanoes whereas, the sedimentary sequence consists of
alluvial, lacustrine and eoline deposits. The Geological Map of the study area are shown below
with the symbol in the legend above has the following meanings

3.4. Structure

The Afar depression is divided into north, central, and south sectors based on its geology and
geography (Tesfaye et al., 2003).The Tendaho-Gobbad discontinuity separates central Afar from
southern Afar (Ebinger & Hayward, 1996). The area is tectonically active indicated by young
faults and the presence of hot springs, fumaroles, steaming ground and fossil hydrothermal
manifestations. NW-SE running mega lineament/faults are crossed the Tendaho-Dubti area,
which is responsible for the formation of the so-called Tendaho Graben. This graben is a flat-
lying ground filled mainly by Fluvo-Lacustrine sediment, having a general NW-SE direction and
4000 Km2 area coverage.

26
The studied region which is in the central part of Afar is affected by different generations of
tectonics. The rift valley and adjacent escarpments are extremely faulted. The fault systems in
these regions are parallel and sub parallel to the axis of the rift, dominantly NE SW (Giday
Woldegabriel et al., 1990). In central and eastern Afar, elongated graben structures (e.g.,
Abhe/Gob Ad, Hanle/Dobi, Tendaho/Dubti, Gaggade, filled by Pleistocene fluvial-lacustrine
deposits are related to the axial .In geothermal drillings in the Tendaho basin, more than
500moffine-grained Pleistocene sediments have been found alternating with basalts (Battistelli et
al., 2002).

Figure 3.2 : Geological and structural map of study area (source, MWIR)

27
 )

3.5. Hydrogeology

In Ethiopia, access to safe water in arid and semi-arid areas is depend on the availability of deep
wells and dugs at shallow ranges along Wadis and fracture zones. In the Ethiopian rift valley,
hydraulic conductivity of water-bearing formations varies significantly among water wells at
only a few hundred meters distance from each Other; (Tenalem , 1998). Groundwater flow is of
key importance in the Awash Basin both as a major source of water supply for people and
because of its impact on hydrographs, especially during the dry period. Highland's fractured
volcanic cover is favorable for groundwater recharge processes (Tenalem, et al., 2008). Thus,
groundwater recharge from the highlands is substantial. Groundwater gradually percolates into
the lower aquifers through large marginal faults before it reaches the rift floor (Tenalem, 2001).
In the upper and middle parts of the valley, the groundwater levels range between 30 and 70 m.
The levels drop to lower than 200m in some areas in the southern corner of the Awash Valley.

According to the study by Gutema Megersa &Endalkachew Getaneh( 2006)on «Geological,

Surface Hydrothermal Alteration and Geothermal Mapping of Dubti-Semera area, Tendaho
Geothermal Field», the following hydrogeological aspects was noticed :

 Porous aquifer of quaternary sediments and fractured basaltic rock intercalation (major
geothermal aquifer,

 Moderately to highly fractured, slightly weathered basalt: Stratified Rift Margin and
Semera basaltic rock units.

 Moderately fractured, weakly weathered to fresh basalt (of Geblaytu and Asboda areas)
and also the alignment of the surface manifestations in Ayrobera and Dubti areas is also
clearly indicative of a series of steps fractures/faults trending in NW-SE direction
underneath. Such geological structures are deeply rooted and reflect the same situation
(effect) on the deep subsurface of the whole Tendaho Rift. These two factors, rifting (up
doming) and block forming nature of fractures influence the drainage and groundwater
flow of the area (both on shallow and esp. deep aquifers/reservoirs).

28
  Infiltration and water circulation is relatively easy on shallow reservoir/aquifer in the
axial part through geologic structures; recharge is mainly from Awash River and directly
from precipitation. Whereas, infiltration and groundwater circulation at depth (deep
reservoir) is minimal because of the two effect

Figure 3.3: Hydrogeological map of the study area ( Source, MWIR)

29
 4. MATERIALS AND METHODS
4.1 Data collection, Sampling and In-situ measurements

4.1.1 Data collection

The study aims is to determine the groundwater flow dynamics, surface water -groundwater
interaction and solute transport modeling of lower awash basin. Since the study area is found in
the tectonically active Ethiopian Rift system, which has a complex hydrogeological system,
integrated scientific approach such as Hydrochemical, Isotopic, Hydrogeochemical modeling
using PHREEQC and hydrogeological modeling using MODFLOW / MT3D will employ.

The study has plan to start the research by collecting secondary data, geological and
hydrogeological from geological survey of Ethiopia, collecting meteorological from national
metrological agency , hydrological data from ministry of water , irrigation and energy ,
Remote sensing (RS) imagery and derived products, such as Digital Elevation Models
(DEMs), LANDSAT, and Sentinel 2 image. Both DEM and satellite images will be freely
downloaded from USGS/NASA servers. The Topo-sheet of the area will be collected from the
Ethiopian Mapping Agency. There will be field observations using GPS (Global Positioning
System) to get the ground truth points for image classification and accuracy assessment

4.1.2. Sampling and In-situ measurements

Judgment sampling method will use for the locations of water sampling points based on from
different rock formations, their location with respect to different geologic structures and the
sampling locations will subdivided into three physiographic regions: the highland, escarpment
and rift floor based on the DEM and the geomorphology of the study area. Samples in each
physiographic region will group into three categories depending on the depth and temperature of
groundwater: shallow, deep and thermal groundwater. Sampling locations will record using a
potable GPS device prior to sampling.

In this research, water samples will collect from rainfall, from deep wells, from shallow wells,
from springs, from river and from lakes based on accessibility in cleaned polyethylene bottles..
Wells will pump for a minutes to eliminate the influence from stagnant water .The sampling

30
bottles will repeatedly rinse with the water to be sampled and then completely fill leaving no
space for air. The rubber stoppers will tightly close and plaster in order to avoid isotopic
exchange with the air and the bottle will label. Samples for cations and anions will filter through
cellulose acetate filters. The sample in a sample bottle will contain enough nitric acid to adjust
the pH to less than 2. These preservation measures are necessary to prevent the metal ions
coming out of solution or forming complexes with organic or other ligands in the water before
reaching the laboratory.
Samples of 1 liter volume will collect for δ18O and δD analyses. To further avoid any diffusive
and evaporative losses from the samples bottles, they will tightly seal for isotopic analysis.

14
Samples of volume between 50 and 60 liters will collect for C analysis. The pH levels of the
water sample will adjusted to 11 using NaOH salt, BaCl2 salt of 100 to 115 g will add and the
samples will shake and left for a day for inorganic carbon to precipitate. The precipitated
inorganic dissolved carbon in the form of BaCO3 will then kept in a plastic container of 1 liter
size and sealed in order to avoid contamination with atmospheric CO2.

Before collecting a sample, the static water level at each borehole and physicochemical
parameters such as pH, temperature, and electrical conductivity (EC) will measure in the field
using depth meter, handheld pH and EC meters respectively. The pH electrode will calibrate
using standard pH 4, 7 and 10 buffer solutions.

4.2. Analytical techniques

4.2.1. Stable Isotopes

Stable water isotope ratios will analyze using a liquid water isotope analyzer. Samples will
analyze against reference values calibrated to Vienna Standard Mean Ocean Water. The Liquid –
Water Isotope Analyzer (LWIA) use high resolution laser absorption spectroscopy technique and
simultaneously measure stable isotope ratio of deuterium (2H / H) and (18O/16 O in liquid water
samples with salinity less than 4%. The equipment is equipped with an auto sampler –auto
injector system that facilitates continuous stable isotope monitoring with minimal user
involvement; thus, provide faster and timely generation of results (Lagura, Christianne F.,
&Urbino, Guima A. (2011).

31
4.2.3. Radon (Rn-222)
The portable radon-in-gas monitor RAD-7 will use for on-site measuring radon activities in the
atmosphere and in water (Burnett and Dulaiova, 2003). The RAD-7 setup allows radon
extraction from a continuously running water pump stream into a closed gas loop which is
pumped through the RAD-7 detection chamber. Radon extraction is accomplished by spraying
the water into a closed air tight plastic cylinder that is part of the closed gas loop.
Radon activities will measure at systematically selected points along the flow paths of the Awash
River, its tributary streams and lakes. Each measurement will carry out for one hour including four
cycles of 15 minutes duration.
4.2.4 Radioactive Carbon (14C)
14
C activity will measure using accelerator mass spectrometry (AMS) and expressed as
13
percentage modern carbon (pmc) while C will measure using an isotope ratio mass
spectrometer (IRMS) and expressed as permil (‰) in the form of CO2 gas.

4.2.5. Hydrochemistry

Water samples will be analyzed for major and trace elements like Na, K, Ca, Mg, F, Cl, NO3-,
HCO3-, SO42-, Fe, Mn, As, Al, Mo, Cr. Major and minor cations will analyze by multi-element
analyzer inductively coupled plasma -optical emission spectrometry (ICP-OES and trace
elements will measure by inductively coupled plasma–mass spectrometer (ICP-MS; equipped
with an ultrasonic nebulization. The ICP-MS will calibrate with multi-element solutions. Anions
will analyze by ion chromatography, HPLC High performance liquid chromatography

32
 Data Collecting

Primary Data Secondary Data

Geological,
Hydrogeological
Hydrochemical &isotope
Collecting of GWL Geological, structural, Geo-
data
water samples measurement morphological observation
&understanding observation

Rinsing the sampling bottle

with the water to be sampled Data input for Modeling

 Model setup & run

 Model calibration
Filter samples Unfilter samples  Model verification
 Model prediction for solute transport
Acidify the modeling
samples for
cations &anions Stable isotope Radioactive In-situ
18 O &2H isotope 14C Measurement of
Rn-222
activities PH,
EC& Temp
Lab analysis of Lab analysis of
major & trace anions using Ion
metals using Lab analysis
chromatography using a liquid Lab analysis of 14C
ICP-MS
water isotope using Accelerator
analyzer mass spectrometry
(AMS)
Hydrochemical data analysis
&interpretation & Geochemical Isotope data analysis and interpretation Flow and solute
Modeling transport Modeling

Ground water flow modeling and solute transport understood

Figure 4.1: Schematic flow chart that shows workflow

33
4.3. Determining the mechanism of recharge and discharge

4.3.1. Mechanism of recharge

4.3.1.1. Stable isotope

Interpretation of isotope data will be carried by plotting the data on the traditional d18O versus
d2H graph along with the local and global meteoric water lines. Their isotopic composition
(deuterium and oxygen-18) will often follow the global meteoric water line (GMWL) (Craig,
1961)). The isotope depletion typically follows an equilibrium line defined by the equation

δD = 8 x δ18O + 10‰ SMOW Equation --------3

( ⁄ ) ( ⁄ )
⁄ Equation ---------4
( ⁄ )

18 ⁄ ) ⁄ )
O ⁄ ⁄ )
----------Equation5

The resulting stable isotope data will interpret by plotting them with the global meteoric water
line (GMWL), which was created for the first time by Craig (1961), and the local meteoric water
line (LMWL) of Addis Ababa (Seifu Kebede et al., 2005). For the interpretation of stable isotope
ratios, the meteoric water line (MWL) will be calculate by least squares regression using
isotopic values from different stations The variations in stable isotope values of water samples
with respect to altitude, depth and geology will critically analyze by using cross plots and
observing their spatial distribution on maps. Afterwards, the observed patterns will use to
identify recharge and discharge areas and recharge mechanism, different groundwater flow
systems and the surface-water/groundwater interaction trends.
A graph of δD and δ18Ο values of water samples will be use to distinguish the various origins of
water. a comparison of the isotopic signature and electrical conductivity of the water samples
collected in different parts of the basin, varying water types with varying isotopic signatures can
be delineated. Clear spatial distribution of the isotopic signature and electrical conductivity of the
water samples indicates the spatial variability of the water type and the recharge– discharge
relationship in the basin.

34
4.3.2. Discharge condition

4.3.2.1. Radon (222 Rn)

Radon is much more enriched in groundwater when compared to surface waters, typically 1000-
fold (Dimova & Burnett, 2011). Because of its un reactive nature and short half-life (T1/2 = 3.83
d) and is produced in the subsurface by the radioactive decay of uranium-series isotopes
222 222
Using Rn values, spatial distribution maps will be generated, considering that low Rn
222
values in groundwater could be qualitative indicators of a losing stream, whereas high Rn
values in superficial water in specific sections of the river are considered to be indicators of
gaining stream conditions (Green & Stewart, 2008)/ 222Rn is an excellent tracer to identify areas
of significant groundwater discharge.

4.3.3. Assessing surface water groundwater interaction

4.3.3.1. Hydrochemistry
Hydrochemical parameters will employ to investigate the interaction between groundwater and
surface water. The data will analyze using multivariate static analysis methods like Hierarchal
cluster analysis. Q-mode hierarchical cluster analysis (HCA) has been proven to provide a
suitable basis for objective classification of water composition into hydrochemical facies (Meng
& Maynard, 2001). Q-mode factor analysis and cluster analysis will apply to the data set. This is
because a statistical approach can not only point out the key parameters that are responsible for
significant variations in the overall chemistry between different set of sampling data (PCA) but
also can aptly illustrate the relationship between different sampling locations based on their
similarity, it will be used in this study as a complementary technique to characterize SW-GW
relationships

The accuracy of the analysis results will check via charge balance error(CBE) . Generally
speaking, the relative error should be within ±5%, i.e.

∑𝐶 𝑖 ∑ 𝑖 ⁄∑ 𝐶 𝑖 ∑ 𝑖

If the CBE is less than 5%, it is good and acceptable and some samples up to 10% CBE could be
considered for analysis and interpretation in different studies (Ravikumar et al., 2011)

35
4.3.3.2. Isotope (deuterium, oxygen-18)
Isotope hydrology is a proven tool in understanding hydrological processes like surface water
groundwater interaction. The power of isotopes of water is that given the isotopic composition of
meteoric waters will be used to investigate groundwater- surface water interaction.

4.3.3.3. Radon (222Rn) Isotope

Radon is abundant in groundwater but has an almost negligible concentration in surface water
due to a short half-life of 3.8 days (Cecil & Green, 2000) and rapid loss to the atmosphere
through degassing (Garcia-Vindas & Monnin, 2005).This contrast in radon concentration
between the groundwater and surface water enables radon to be ideal to measure surface water
groundwater interaction. Surface water which have an elevated concentration of radon indicate
the location where the groundwater is discharging into surface water

4.4. Determining the sources and age of groundwater

4.4.1. Sources of groundwater

4.4.1. 1. Stable isotopes

In the last few decades, the isotopic signatures of meteoric waters, particularly the ratio 18O/16O,
have become a key tracer, intensively used in hydrogeological studies as a basis for the
elaboration of the conceptual hydrodynamic model. This method will be used to know the
recharge source, recharge mechanisms by using fractionation principles. Deuterium and
oxygen.18 will fractionate during the process of evaporation and condensation. They are
relatively enriched in the liquid phase and depleted in the vapor phase. Hence, it helps to identify
different sources of recharge and identify the variations in the isotopic composition of
groundwater, runoff, and rainwater

The isotopic composition of groundwater (expressed as abundance of oxygen-18 and deuterium)

is determined by the isotopic composition of recharge. If most of the recharge is derived from
direct infiltration of precipitation, the groundwater will reflect the isotopic composition of that
precipitation. However, if most of the recharge is derived from surface water (rivers or lakes)
instead of from precipitation, the groundwater will reflect the mean isotopic composition of the
contributing river or lake.

36
4.4.2. Age of groundwater

4.4.2.1. Radioactive Carbon

14
The radioactive isotope C has a life of 5730 years. It is produced by the interaction of cosmic
rays with atmospheric gases in the upper atmosphere and mixing within the upper atmosphere

14
C activity will express as percentage modern carbon (pmc) while 13C as permil (‰) in the form
14
of CO2gases. The C activity will correct using δ13C, and the apparent age of the groundwater
samples will calculate using Pearson's model. The procedure is a modification of the Pearson
method (Pearson & Hanshaw, 1970) is using δ13C data as the basis for correction calculations.
Conventional groundwater age, if the initial concentration of the parent is known and has been
remained constant in the past and the system is closed, can be calculated using the relation:

* + Equation ------------6

The dilution of 14C through reaction is accounted for in the decay equation by the dilution factor,
q and the equation then becomes

* + Equation ------------7

Where is a measure value of 13C in groundwater?

𝑖 D13C of the calcite being dissolved
13
Csoil is 13C of the soil CO2
is initial value of recharge water
Since, values for d13Csoil and d13Ccarb will not generate by this work, they will take from
Bretzler et al. (2011). The value for d13Csoil and for d13Ccarb will base on pH of recharge water
and the corresponding value of enrichment factor will obtain from the graph (Clark and Fritz,
1997). These values together with d13CDIC results for the groundwater samples will use to
estimate dilution factor for each sample. so as to calculate 14C age with Pearson model

37
 Collecting of water samples, In-situ
Parameter Measurement& GWL
measurement

Hydrochemical and isotope analysis of water samples in the laboratory

Data Processing

Hydrochemical Data Isotopic Data

Stable ,18O &2 H

Analysis using IBM SPSS Radiogenic

Calculate isotopic ratio 14

C 222
 GW Flow Direction Rn
 GW Recharge system
 SW-GW Interaction
 Calculating the apparent Measuring the Rn
14
age using C activities
activity using
based on Pearson’s model
18
LMWL O & H of
2 RAD 7 in the field
precipitation data

Residence time of groundwater

Plots deviation of
isotopic ratio against
LMWL

 GW discharge condition
 Recharge sources &
mechanism  SW-GW Interaction
 SW –GW Interaction

Figure 4.2: Schematic diagram of recharge-discharge condition of groundwater

4.5. Characterizing the hydrochemical evolution, major geochemical processes, and

water quality of groundwater

Hydrogeochemical research aims to study a multivariate problem. Each water sample has
multiple hydrochemical variables. Multivariate statistical analysis is used to quantify and
independently classify different types of groundwater samples, and the method is used to
determine the correlation between chemical parameters and groundwater samples

38
In this study, Multivariate statistical analysis like Hierarchical Cluster Analysis (HCA) and
Principal Component Analysis (PCA),) will apply to better in the interpretation of
hydrogeochemical evolution including inverse geochemical modeling

Hydrochemical variables will utilize in this analysis. For statistical analysis, all the variables
which are not normally distributed will be log-transformed and more closely correspond to
normally distributed data. Subsequently, they will standardize to their standard scores (z-scores)
as described by Güler et al. (2002). Hydrochemical results of all samples will statistically
analyzed by using the software STATISTICA

4.5.1. Hierarchical Cluster Analysis (HCA)

The hierarchical cluster analysis will perform with variable hydrochemical parameters of
different samples. Individual samples will be compared with the specified similarity/
dissimilarity, using the selected Ward’s linkage method, and will group into clusters. Ward’s
linkage method which iteratively links similar samples by using the distance matrix A
classification scheme using Euclidean distance for similarity measurement, together with Ward’s
method for linkage, produces the most distinctive groups where each member within the group is
more similar to its fellow members than to any member outside the group (Güler et al. 2002).

Assumptions of the HCA technique include homoscedasticity (equal variance) and normal
distribution of the variables (Alther 1979). To determine the relation between water samples, the
standardized data matrix will import into the statistics package. STATISTICA offers similarity/
dissimilarity measurements and linkage methods

4.5.2. Principal Component Analysis (PCA)

Principal Component Analysis (PCA) is a mathematical technique used for reducing data and
deciphering patterns within large datasets(Wold et al., 1987; (O’Shea & Jankowski, 2006). PCA
will use to reduce the number of variables, investigate the degree of continuity or clustering of
the samples, and identify the variables most important to separating the groups; in effect,
extracting the factors that control the chemical variability.
In PCA, the main components of groundwater data will extracted by applying the Kaiser
normalization criterion to the maximum variance method to rotate the maximum component to
reduce the dimensionality, extract the main influencing factors
39
The procedure begins with principal component analysis (PCA) to determine what factors
(groups of parameters) account for the numerical variation of the clusters. This step serves to
provide insight into the hydrochemical processes and sources of solutes. Next procedure is
hierarchical cluster analysis (HCA) of the data to cluster similar samples. The statistical clusters
are examined for spatial coherence to verify that the clusters have a physical basis.
Results of multivariate statistical analysis will combine with the geomorphological and
hydrogeological knowledge of the study area in order to give a hydrological explanation of each
data cluster.

4.5.3. Inverse Geochemical Modeling

Inverse geochemical modeling is commonly used to reconstruct geochemical evolution of

groundwater from one point in an aquifer to another point located in the inverse direction along
the groundwater flow path. Recently, inverse geochemical modeling has been used to investigate
the chemical evolution of groundwater along the flow path by various investigators (Plummer et
al., 1990; Guler et al., 2002).

This method will be used to identify the chemical evolution of groundwater in the study area.
Using this method the type and amount of minerals in moles that can dissolve or precipitate
along a groundwater flow path will be determine provided that the flow path can be selected
depending on available general hydrogeological information. PHREEQC will use to calculate
aqueous speciation and mineral saturation indices for samples along the topographic flow path.
Inverse modeling in PHREEQC uses the mass-balance approach to calculate all the
stoichiometrically available reactions that can produce the observed chemical changes between
end-member waters .(Glynn & Plummer, 2005).
Mean values of the HCA-defined clusters will provide starting and ending water compositions
for the inverse models. Using the mean values of the clusters preserves information about
relative differences in abundance between ions. Minerals used in the inverse geochemical models
will be limited to those present in the study area.
The saturation index will also use as indicator in hydrogeochemical status. It describes the
saturation status of minerals in the groundwater. When =0, the minerals in the aqueous solution
are in equilibrium status; when <0, the minerals in the aqueous solution have not reached

40
saturation, and bear on a dissolution trend; when , a >0 supersaturated status of minerals in the
aqueous solution is indicated and mineral deposition will occur (Qian and Ma 2005; Luo et al.
2008). The saturation index ( ) can be calculated using :

Where is the relevant ion activity product in a mineral dissolution reaction, which can be
obtained by multiplying the ion activity coefficient and composition concentration ; and K is
the equilibrium constant of mineral dissolution at a certain temperature.

4.5.4. Water Quality Index (WQI)

Water quality index method is a powerful tool that enables easy to measure of the quality of
water and WQI, which is calculated using the weighted arithmetic index method will be use for
water quality assessment and GIS will also use for spatial water quality mapping.

∑
∑
, Where qi=quality rating (sub index) of ith water quality parameter

wi= unit weight of ith water quality parameter;∑ =1

( )

Where vi= estimated value of the ith parameter vio= ideal value of the ith parameter

In most cases, vio=0 except for pH

The unit weight (wi), which

41
 Collection of representative water samples

Physico-chemical laboratory analysis

Water quality analysis

Water quality index Spatial water quality Multivariate Aqua Chem

map using GIS statistical Analysis

Principal component analysis (PCA) Piper &Gibbs plots

Hierarchical cluster analysis (HCA)

Inverse geochemical modeling using PHREEQC Hydrogeochemical facies

Equilibrium chemical species and Hydrogeochemical

saturation index Water Types
processes

Hydrogeochemical evolution characterization and processes

Figure 4.3: Schematic diagram of hydrogeochemical evolution and processes

4.6. Develop flow and transport modeling

4.6.1. Ground Water Flow Model

4.6.1.1. Model Conceptualization and Input Data

Conceptual model (conceptualization), is a description of the known physical features and the
groundwater flow processes within the area of interest. The conceptual model is a simplified

42
representation of the features governing groundwater flow in the aquifer that consisting of a set
of assumptions that verbally describe the system’s composition (Kumar, 2015).,

A conceptual model can subsequently be populated with project-specific characteristics, such as

groundwater levels, recharge zones, and connectivity between withdrawal points and discharge
zones, and finally will be used for numerical modeling.(Izady et al., 2014)

The hydraulic properties associated with subsurface materials largely control the flow of
groundwater and migration of contaminants. Hydraulic properties of interest include: hydraulic
conductivity, aquifer storage (storativity and specific yield) porosity and recharge, and discharge
and groundwater abstraction through pumping, primary water level data will be collected in field
and secondary data will collect in the respective organization
Boundary conditions are necessary in the model to understand how the site specific model
interacts with entire flow system that specifying the head or fluxes. The boundary conditions will
be determined based on the hydraulic condition. Initially these values will be apply in the
conceptual mode. A no-flow boundary condition is set by specifying this flux to be zero
(Anderson et al., 1992). A comprehensive study (e.g., lithology and geology studies) will do in
this research to be able to model the aquifer boundaries (Aquifer geometry). The bottom
boundary (bed rock in the aquifer) will determine with limited previous geophysical data .The
conceptual model of the system will model from the detailed studies of geology, borehole
lithology and water level in wells.

4.6.1.2. Model setup and running

To carry out three dimensional finite numerical modeling , visual MODFLOW code will use for
simulation of flow model to deal dynamics of groundwater that predict the future changes of
heads and change in the flow direction and MT3D for the simulation of solute transport model to
solve the problem of solute transport and the change of their concentration with time.

In order to setup the model in MODFLOW, the area will be divided into a series of grid blocks
or cells. This grid has to be block-centered (that is, the groundwater heads will be computed at
the center of each grid block.). The model will constructed where grid cells, initial head,
boundary conditions, and other aquifer properties are defined. Following the pre-processing of

43
model, hydraulic properties will estimate and model will set for simulations. The ground-water
flow equation will solved using the finite-difference approximation. The flow region is
considered to be subdivided into blocks in which the medium properties are assumed to be
uniform. Coupling MODFLOW with ArcGIS powerful software will use to simulate the
groundwater flow and solute transport

4.6.1.3. Model Calibration

Model calibration is the process of adjusting the model input parameters or flux such as
hydraulic conductivity and recharge so as to match them with the existing field conditions to
obtain a model representation of the processes within some acceptable criteria(Khadri & Pande,
2016). Model calibration will include comparisons between model-simulated conditions and
field conditions for the following data: hydraulic head data, groundwater-flow direction,
hydraulic-head gradient, water mass balance, contaminant concentrations) and migration rates
migration directions and degradation
The purpose of the calibration of a groundwater flow model is to demonstrate that the models
can response field measured heads and flows, which are the calibration values (Anderson et al.,
1992). . Model calibration can be done manually, through trial-and-error, but it is much
easier to do with the help of PEST. This method (PEST) can be considered as stands for
parameter estimation; it is a non-linear inverse modeling code, developed by John Doherty,
Watermark Numerical Computing”. PEST uses a powerful mathematical technique to estimate a
new set of parameters by comparing model results to a set of observations, and provides valuable
insight into the conceptual model (Computing, 2004)
.
PEST calibration can be performing in two ways including zonal and pilot point. The first
approach (i.e., zonal) is the most common one (Aghlmand & Abbasi, 2019)and will apply in this
research .With the zone-based approach, each zone will treat as a parameter. PEST adjusts the
values until good fit is achieved. The results will give an indication of where new zones should
be added(Doherty & Hunt, 2010) . Zonation will adjust as needed, PEST will run again.
Calibration of the model will perform for steady-state in this study because the time series of
groundwater flow are unknown. Typically, the difference between simulated and actual field

44
conditions (residual) should be less than 10 % of the variability in the field data across the model
domain

4.6.1.3.1. Steady State Calibration

Steady state calibration is a process to match the initial heads with the simulated hydraulic heads
by sequential adjustment of model parameters(Shehata et al., 2020). It is a condition in which
inflows are equal to outflows with no change in storage. With steady-state simulations, there are
no observed changes in hydraulic head or contaminant concentration with time for the field
conditions being modeled.
Steady state calibration for the flow model will achieve by comparing the hydraulic heads
obtained from available groundwater level contour maps of the layers and the calculated
hydraulic heads of the MODFLOW simulation in order to simulate the flow lines of the layers.
During calibration, horizontal and vertical hydraulic conductivities and recharge values will
adjust in sequential model runs to match the simulated heads and measured head

4.6.1.3.2. Transient State Calibration

Successful transient calibration depends mainly on the good estimation of hydraulic

conductivities and boundary conditions obtained from the steady state calibration Upon
achieving the satisfactory results from steady state simulation, for transient state calibration
model will run. Transient simulations involve the change in hydraulic head or contaminant
concentration with time Transient models simulate time-dependent problems such as the impact
of stresses over time(Khadri & Pande, 2016). A transient simulation will begin with
representative initial conditions and ends at a specified elapsed model time in which the time will
divide into different stress period.

4.6.1.4. Verification and Validation

Verification is the process of determining that a model implementation accurately represents the
developer’s conceptual description of the model and the solution to the mode and l. Validation is
the process of determining the degree to which a model is an accurate representation of the real
world from the perspective of the intended uses of the model. Verification and validation are

45
processes that collect evidence of a model’s correctness or accuracy for a specific
scenario(Thacker et al., 2004) The available measurement data will split into two groups; one for
calibration and the other for validation. The adjustments to parameters or boundary conditions
will require achieving verification, and then the calibration simulation needs to be re-run, and re-
assessed. This process may need to be repeated until a set of parameters and boundary conditions
is identified that produces a good match to both the calibration and verification data sets. There
are several approaches to validate a model; perhaps the most effective procedure is to use only a
portion of the available record of observed values for calibration. Once the final parameter
values are developed through calibration, simulation will perform for the remaining period of
observed values and goodness-of-fit between recorded and simulated values is reassessed..

4.6.2. Transport flow model

A solute transport model which can be communicated with MODFLOW through data files
MT3D, is used to solve the problem of contaminants transport and the change of their
concentrations with time(Ghoraba et al., 2013) . These models can simulate the migration of
solutes through the subsurface and the boundaries of the system. MT3D will uses for the
simulation of solute transport model to solve the problem of solute transport and the change of
their concentration with time. MT3D is a model for simulation of advection, dispersion and
chemical reactions of contaminants in groundwater flow systems in either two or three
dimensions(Zheng, 1992).

For transport modeling the data requires are: groundwater quality measurements over time,
average groundwater velocities (horizontal and/or vertical), effective porosity, Longitudinal and
Transverse dispersivity

4.6.2.1. MT3D Model setup and running

Transient simulation as well as flow calibration begins with the steady-state initial conditions
with the same boundaries, parameters and methods of advection and ends before or when a new
steady state is reached. Both the time and the stress period will divide into several steps.

46
4.6.2.2. Calibration

The fixed grid system of the transport model will base on the block-centered formulation where
at the center of the cell, the concentration will calculate. The chemical parameters such as
dispersivity are assumed to be uniform over the extent of a cell
Simulated contaminant concentrations will be compared to the measure concentrations in a
stabilized plume in steady state calibration Parameters (such as effective porosity and
dispersivity will be calibrate by matching simulated and observed spatial and/or temporal
distributions of a solute. . In the transient calibration, the model output for various time steps
will be compare to the measure time-series values of contaminant concentrations of
groundwater samples. The solute transport model will calibrate using observed solute
concentrations time trends. Statistical evaluations of residuals will be presented in tabular and
graphical formats. An x-y scatter plot of observed versus simulated concentration of solute will
show the magnitude and bias in residuals

The model will calibrate using parameter estimation tool (PEST) and during calibration process,
parameter values will adjust within predefined ranges until the simulated concentration match the
observed data

4.6.2.3. Model prediction

Groundwater contaminant transport modeling is an interesting tool to use in order to predict the
contamination distribution of a site (Duriez, 2005). Predicted changes in groundwater flow
system or solute transport. Model predictions will conduct in order to evaluate the response of
the model for future scenarios. These scenarios vary in terms of pump rates for the different
operating well groups in the basin.

Predictive contaminant transport simulations will run until the contaminant plume has reached
steady-state (or near steady-state) conditions. Assuming the source and mass loading of the
contaminant to groundwater remains constant (or near constant), at some moment in time the
contaminant plume will reach a maximum size and the shape of the plume will remain relatively
fixed for future times.

47
In Transient numerical simulations aquifer stresses, contaminant source concentrations and mass
loading rates will be vary over time. Model inputs will vary incrementally for a series of
individual simulations to generate transient contaminant transport simulations

Data input Boundary condition

Steady state
MODFLOW Model Set Up
GW flow
model
Steady-State Model Running Parameter adjustment&
Optimization

Calibration

Transient GW Flow Model MODFLOW Model Set Up

Transient Model Running

Parameter Optimization Calibration Drain Scenario Optimization

Validation

Solute Transport Model MT3D Model Set up

Transport Model Calculation

Parameter Optimization Calibration

Transport Model Result

Model Prediction

Figure 4.4: Schematic: Diagram of flow and transport modeling

48
 5. RESEARCH SCHEDULE

Years 2021 2022 2023

Time in Months
No Activities

Jan-Mar

Jan-Mar

Jan-Mar
Oct-Dec

Oct-Dec

Oct-Dec
Apr-Jun

Apr-Jun

Apr-Jun
Jul-Sep

Jul-Sep

Jul-Sep
1 Literature Review
2 Secondary Data Collection
3 Study area delineation
4 Field Data collection of water samples and water level
measurement
5 Laboratory analysis of water hydrochemistry and isotope
6 Data processing
7 Determination of the area and mechanism of recharge and
discharge condition of the groundwater system: Objective I
8 Determination the sources and age of the groundwater
Objective II
9 Manuscript preparation and send to Journal
10 Characterize the hydrochemical evolution, major
geochemical processes : Objective III
11 Manuscript preparation and send to Journal
12 Develop a groundwater flow and solute transport model:
Objective IV
14 Manuscript preparation and send to Journal
15 Document submission

49
 6. BUDGET

I Data/ other purchase Years/ Data point Cost / Sum

(year*station
)
1 Metrological 40/40 25 1000
2 Topographic map 1 500 500
3 Soil map 1 500 500
Sub total 2000
II Field visit No of days Cost Sum
1 Accommodation 30 250 7500
2 transport 30 1500 45000
Sub total 1750 52500
111 Lab Analysis cost No of samples
1 Hydrochemistry of major ions 100 1000 100000
2 Water isotopes 50 1500 75000
3 Sampling Bottles 150 10 1500
Sub total 200 2510 176500
Total 231, 000

50
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