ADDIS ABABA SCIENCE AND TECHNOLOGY UNIVERSITY

POTENTIAL FOR LITHIUM-EXPLOITATION IN

ETHIOPIA: A BASELINE INVESTIGATION ON

POSSIBLE LITHIUM-BRINE AND EVAPORITE

DEPOSITS IN SELECTED MAIN ETHIOPIAN RIFT

LAKES AND NORTHERN DANAKIL DEPRESSION

A MASTER THESIS

BY

ASSNAKE BEKELE

ADVISOR: ROLAND SCHMEROLD (Dr.rer.nat.)

TO

DEPARTMENT OF GEOLOGY

APPLIED SCIENCE COLLEGE

JUNE 2019

ADDIS ABABA, ETHIOPIA

 ADDIS ABABA SCIENCE AND TECHNOLOGY UNIVERSITY

POTENTIAL FOR LITHIUM-EXPLOITATION IN

ETHIOPIA: A BASELINE INVESTIGATION ON

POSSIBLE LITHIUM-BRINE AND EVAPORITE

DEPOSITS IN SELECTED MAIN ETHIOPIAN RIFT

LAKES AND NORTHERN DANAKIL DEPRESSION

By

ASSNAKE BEKELE

Advisor: ROLAND SCHMEROLD (Dr.rer.nat.)

A Thesis Submitted as Partial Fulfillment of the Requirements for the

Degree of Master of Science Degree in Geology (Economic Geology)

To

DEPARTMENT OF GEOLOGY

COLLEGE OF APPLIED SCIENCE

JUNE 2019
ADDIS ABABA, ETHIOPIA
Declaration
I hereby declare that this thesis entitled “Potential for Lithium-Exploitation in
Ethiopia: A Baseline Investigation on possible Lithium-brine and evaporite
deposits in some selected Main Ethiopian Rift lakes and Northern Danakil
Depression” was prepared by me, with the guidance of my advisor Roland
Schmerold (Dr.rer.nat.). The work contained herein is my own except where
explicitly stated otherwise in the text, and that this work has not been submitted, in
whole or in part, for any other degree or professional qualification. Parts of this work
have been submitted for publication.

Author: Signature, Date:

Assnake Bekele Habtemikael

Witnessed by:

Name of student advisor: Signature, Date:

Roland Schmerold (Dr.rer.nat.)

II
Certification
This is to certify that the thesis prepared by Mr. Assnake Bekele entitled “Potential
for Lithium-Exploitation in Ethiopia: A Baseline Investigation on Possible
Lithium-Brine and Evaporite Deposits in selected MER lakes and Northern
Danakil Depression” and submitted as a partial fulfillment for the Award of the
Degree of Master of Science complies with the regulations of Addis Ababa Science
and Technology University and meets the accepted standards with respect to
originality, content and quality.

Signed by Examining Board:

Advisor: Signature Date

………………………………………………………………………………………
External Examiner: Signature Date
………………………………………………………………………………………
Internal Examiner: Signature Date
………………………………………………………………………………………
DGC Chairperson: Signature Date
………………………………………………………………………………………
Associate Dean for Signature Date
Graduate Programs:
………………………………………………………………………………………

III
Abstract
Lithium is a metal with increasing demand on the global market mainly for its
application in lithium ion battery for electric cars. Ethiopia has a potential for lithium
deposits related with pegmatites but also lithium brine deposits may be expected in
the country.

The current research covered the Danakil depression and selected lakes of the Main
Ethiopian Rift to check the indications of lithium brine and evaporite occurrences in
Ethiopia. To achieve the research objectives, brines and evaporite rock samples were
collected from the proposed area for geochemical analysis of lithium by using ICP-
AES and AAS test method. In addition petrographic studies were used to correlate
with the geochemical results of the evaporite samples and a model for the possible
source of lithium in Danakil was developed. Lithium values in water samples from the
MER lakes like Chew Bahir, Chamo, Abaya, Shala, Abijata show elevated Na and K
values but no significant lithium concentrations above the average Li content in
surface waters. Lithium shows enhancement in the residual brines of the multi stage
evaporation pond in Abijata-Sahala soda ash production. The brine produced during
precipitation of trona and halite reach values of 0.009 ppm Li still well below
economically extractable concentrations. Lithium concentrations are enhanced in
brine lakes, brine ponds and hot springs of the Danakil depression. The highest
concentrations reach 20 ppm of Li in hot springs of Dallol. Lithium concentrations in
drill core samples from the Danakil show a Li-accumulation up to 20-40 ppm in the
Carnallite and Bischofite horizons of the potash bearing evaporite sequence. Lithium
is being discharged by hot springs derived either from deep cycling of hydrothermal
meteoric waters or partly from juvenile water associated with the recent volcanic
activity. The current hydrological situation suggests also the possibility of Li being
introduced in to the Danakil depression by surface run off from the western
escarpment, with various suitable source rock types for dissolved lithium. In addition
the variation of Li-content in the different layers of the Late Tertiary/ Quaternary
evaporite sequence indicates the accumulation of Li during sea water evaporation
until the late stage of precipitation of potassium and magnesium chlorides.
The total estimated lithium content at 50% of recovery is about 3 million tons of
lithium associated with the potash horizons in Danakil represents an inferred mineral
resource large enough for economic exploitation as byproduct of the potash solution
mining projects if lithium extraction approaches lower cut-off grades as the current
200 ppm.

Key Words: Lithium, Brines, Dallol, Main Ethiopian Rift, Ethiopia.

IV
Acknowledgment
The Addis Ababa Science and Technology University is thanked for providing me the
opportunity and necessary support to pursue my Master studies. I would like to
acknowledge my advisor Roland Schmerold (PhD) for his valuable advice,
constructive comment, suggestion, guidance and are dedicated to me from the
beginning to the end of my study.

This thesis work is carried out in connection with four Industry partners: namely
Circum Mineral Potash, Yara Dallol BV, Tanamru Chemical Industrial PLC and
Abijata-Shala Soda Ash Project and they are highly acknowledged. I would like thank
those companies’ staff members who assisted me by sharing relevant data, facilitating
access to the site visit, giving their time and expertise to offer great input for this
work. I would like to express my deepest gratitude to Ato Yonas Bekele/ General
Manager, Merhawit Teklehaymanot and Solomon staff member of Circum Potash. I
would also like to extend my gratitude to Gebreegziabher Mekonen/ General
Manager, Henok Tsegaye/ Site manager, Bereket Ayele and Said Mohahmed/ site
geologist of Yara Dallol BV. I would also like to sincerely acknowledge Xing Zhang/
General Manager and Yonatan Amare staff member of Tanarmu Chemical Industrial
P.L.C and Dr. Berhanu/ General Manager and Mr. Tadesse/ site manager of Abijata
Soda Ash company. I would also thank the Geological Survey of Ethiopia and
Ministry of Mine, Petroleum and Natural Gas for their support during data collection.
Finally, I would like to acknowledge Dr. Tesfaye (Current Head department of
Geology) and Mr. Gemechu Bedassa for their critical comments and suggestions. All
my friends and staff members of AASTU's geology department are highly
acknowledged and any omission in this brief acknowledgement does not mean lack of
gratitude.

V
 Table of Contents
Declaration ................................................................................................................................. II
Certification .............................................................................................................................. III
Abstract ..................................................................................................................................... IV
Acknowledgment ....................................................................................................................... V
List of Figures ......................................................................................................................... VIII
List of Tables ............................................................................................................................. X
List of Acronyms .................................................................................................................... VIII
CHAPTER ONE ........................................................................................................................ 1
1.0 Introduction .......................................................................................................................... 1
1.1 Background ................................................................................................................ 1
1.2. Description of the Study Areas ....................................................................................... 3
1.2.1 General Location of the study area ........................................................................... 3
1.2.2 Accessibility.............................................................................................................. 5
1.3 Climate and drainage pattern ........................................................................................... 5
1.4 Statement of the problem ................................................................................................. 6
1.5 Objective of the Research ................................................................................................ 7
1.5.1 General Objective ......................................................................................................... 7
1.5.1.1 Specific objective ................................................................................................... 7
1.6 Methodology .................................................................................................................... 7
1.6.1 Office Work Approach ............................................................................................. 7
1.6.2 Field Work Approach ............................................................................................... 8
1.6.3 Post Field Approach .................................................................................................. 9
1.7 Previous Work and Present Study.................................................................................. 10
1.8. Thesis Overview ........................................................................................................... 11
CHAPTER TWO ..................................................................................................................... 12
2. Regional Geological Setting and Rift Basins ....................................................................... 12
2.1 Main Ethiopian Rift System (MER) .............................................................................. 12
2.2 Afar Depression ............................................................................................................. 14
CHAPTER THREE ................................................................................................................. 17
3.0 Geology of the Study Areas ............................................................................................... 17
3.1. Chew Bahir Basin ......................................................................................................... 17
3.2 Zeway-Shala Basin ........................................................................................................ 18
3.3 Geology of the Danakil area .......................................................................................... 19

VI
 3.3.1 Drill-Core Based Geology of the Danakil Evaporite units ..................................... 22
CHAPTER FOUR.................................................................................................................... 27
4.0 General Information and Background Description on Lithium ......................................... 27
4.1. Introduction ................................................................................................................... 27
4.2 Genesis of Lithium......................................................................................................... 27
4.2.1 Occurrence and Source of Lithium ......................................................................... 27
4.2.2 Types of Lithium Deposits...................................................................................... 28
4.3 Economic Concentrations of Lithium in mineral deposits............................................. 31
4.4 World Lithium Production, Consumption and Demand Forecast .................................. 32
4.5 General Condition for the formation of Lithium Brine Deposits and the Situation in
Ethiopia ................................................................................................................................ 32
4.8 Prior Work on Lithium-Brine Deposits Exploration of Ethiopia ................................... 34
CHAPTER FIVE ..................................................................................................................... 36
5.0 Geochemical Results .......................................................................................................... 36
5.1 Geochemistry of Brines (Danakil and MER Lakes) ...................................................... 36
5.2 Geochemistry of Rocks .................................................................................................. 45
CHAPTER SIX ........................................................................................................................ 52
6.0 Comments on Economic Extraction of Lithium during Potash Mining in Danakil
Depression ............................................................................................................................... 52
6.1 Present Status of Lithium-Brine Extraction Technologies............................................. 52
6.2 Possibility of Lithium Extraction in the Danakil Potash Project ................................... 54
CHAPTER SEVEN ................................................................................................................. 56
7. Discussion ............................................................................................................................ 56
7.1 Brines (Danakil Depression) .......................................................................................... 56
7.2 Brines (MER Lakes) ...................................................................................................... 60
7.3 Comparison of some selected world known lithium brine deposit with the occurrence in
Ethiopia ................................................................................................................................ 61
7.4 Rock samples from Danakil depression ......................................................................... 66
7.5 Petrographic observations .............................................................................................. 67
7.6 Schematic Model of the Danakil Depression ................................................................. 70
CHAPTER EIGHT .................................................................................................................. 72
8.0 Conclusion and Recommendation ..................................................................................... 72
8.1 Conclusion/ Interpretation ............................................................................................. 72
8.2 Recommendations .......................................................................................................... 74
Reference: ................................................................................................................................ 75

VII
 List of Figures
Figure 1. 1: Location map of the lake regions and surrounding of Dallol: A) Danakil
depression (Containing parts of Lake Afdera and Dallol areas part of Circum and
Yara potash license areas); B) Lake Abijata-Shala, and C) Lake Chew Bahir. The Red
Cross indicates the location of the brine samples. ........................................................ 4
Figure 1. 2: Accessibility Map of the Study Areas. .................................................................. 5

Figure 2. 1: Digital elevation model (SRTM data) of the Main Ethiopian Rift showing the
main rift segments (Corti, 2009): (from north to south) Southern Afar (S-Afar),
Northern Main Ethiopian Rift (NMER), Central Main Ethiopian Rift (CMER) and
Southern Main Ethiopian Rift (SMER). BRZ: Broadly Rifted Zone; CB: Chew Bahir
Rift; GB: Gofa Basin and Range. B) Simplified geological map of Ethiopia (Abbate
et al., 2015; http://www.gse.gov.et/index.php/2016/09/03/overview-3/). .................. 14
Figure 2. 2: A) Location of the Afar depression and local fault lines in the map of East Africa
showing some of the historically active volcanoes (red triangles) and the Afar
Triangle. The red triangles show historically active volcanoes (Source: USGS,
1999,http://pubs.usgs.gov/gip/dynamic/East_Africa.html). B) Simplified geologic
map of the Afar depression (Beyene and Abdelsalam, 2005)..................................... 16

Figure 3. 1: Geological map for the catchment of the lake Chew Bahir (Foerster et al., 2012
and reference therein). ................................................................................................ 17
Figure 3. 2: Simplified geological map of the Lakes Region in the CMER (Adapted from
Benvenuti and Carnicelli, 2015). The details and main characteristics of each
Synthem are described by Benvenuti et al., (2002) and Benvenuti and Carnicelli,
(2015). ......................................................................................................................... 18
Figure 3. 3: Simplified Geological Map of the northern Danakil area (Adapted from Solomon
and others, 2011). The green triangle represents the location of surface out crop rock
salt samples; the red crosses indicates the location of brines and hot springs and the
light blue star represents the location of the Drill holes. Descriptions of the samples
located on the geological map are given in table 3.1. ................................................. 19
Figure 3. 4: Field photographs showing part of the Dallol and the surrounding area. (A) Part
of the western escarpment, alluvial fan and transition zone, (B) Salt flat, (C) Part of
the ground water system in the salt flat, (D) Hot spring with sulfur occurrence at the
top of mount Dallol, (E) Pond in the transition zone, (F) Circular depression in the
salt flat, (G) Side of Black mountain with gypsum, halite, silt and clay deposits and
(H) Elevated circular depression. ................................................................................ 21
Figure 3. 5: The Generalized Stratigraphic Section of the Potash Bearing Evaporite Deposit
of Circum and Yara Potash License Areas. ................................................................ 23
Figure 3. 6: The Generalized Stratigraphic Section of the Potash Bearing Evaporite Deposit
of the Danakil depression of Musley area, Dallol, Ethiopia and part of the Circum and
Yara Potash License Areas (Holwerda and Hutchinso, 1968; Muzvondiwa et al, 2015;
Warren, 2016). ............................................................................................................ 26

VIII
Figure 4. 1: World map of lithium brine deposits with inset showing detail in South America.
Histogram showing the bimodal latitudinal distribution of Li-brine deposit in northern
and southern arid belts (Adapted from Bradley et al., 2013). ..................................... 29
Figure 4. 2: World map showing the locations of lithium-cesium-tantalum (LCT) pegmatite
deposits or districts, including smaller districts in the United States. The symbols are
color-coded by age. Huge deposits are represented by larger symbols (Bradley and
McCauley 2016; Bradley et al., 2017). ....................................................................... 31
Figure 4. 3: USGS Schematic deposit model for lithium brines deposit showing part of a
closed-basin system consisting of interconnected sub-basins. The sub-basin
containing the salar is the lowest (Bradley et al., 2013). ............................................ 33
Figure 4. 4: World map showing Lithium and CaCl2 brine occurrences (Warren, 2016). The
Red stars indicate operations that are on the stages of extracting lithium brines in a
saline setting. The green star indicates locations of possible future lithium brine
resources. The purple circle indicates an active CaCl2 brine operation; green squares
indicate other sites of CaCl2 that may be a future possible CaCl2 brine resource. The
brown circles and green shaded rectangular zones indicate the positions of ancient
marine halite and sulphate basins. .............................................................................. 35

Figure 5. 1: Scatter plot for brine samples (A) Li versus Sr (ppm), (B) Li Vs K (ppm)......... 39
Figure 5. 2: The general outline of lake Afdera and contour map of the lake from its lithium
values, the red cross indicates the location of the sample points with respective
lithium values. The lithium concentration from the lake shows inhomogeous
distribution. The elevated lithium concentration was recorded in North-Eastern part of
the lake, which can be feed by hot springs passing through felsic volcanic rocks that
give rise to relatively high lithium content on that spot. ............................................. 44
Figure 5. 3: Digital elevation map of lake Afdera from its lithium values, the red cross
indicates the location of each sample points with respective lithium values. ............. 45
Figure 5. 4: Scatter plots for rock samples Li Vs Rb and Li Vs F. ......................................... 48
Figure 5. 5: Bore Hole 2 Stratigraphic section Vs linear graph of Li, Rb, F, K2O, MgO, CaO,
Na2O, and SrO. The lithium is enriched in the lower and upper carnallitite unit, which
is the potash bearing horizon. ..................................................................................... 50
Figure 5. 6: Bore Hole 1 Stratigraphic section Vs linear graph of Li, Rb, F, K2O, MgO, CaO,
Na2O, and SrO. ........................................................................................................... 51

Figure 6. 1: Overview of Emerging Brine Technologies. ....................................................... 53

Figure 7. 1: Log scale multi-element plot of (a) Dallol hot spring; (b) Surface brines in the
surrounding of Dallol, and (c) Combined plot of both surface brines and hot springs.
The description of the samples plotted as YD-1A, YD-2A, DL-1A, DL-2A, DL-3A,
DH-1and DH-2 are given in chapter five table 5.1 and 5.2. ....................................... 58
Figure 7. 2: Scatter plot of Li Vs F, K and Sr for Dallol samples. .......................................... 59

IX
Figure 7. 3: Log scale multi-element diagram of the Main Ethiopian Rift lake samples. The
description of the samples CB-01A, CB-02A, CB-03A, CM-01A, WT-01A, AB-01A,
AB-01, AB-02, AB-03 and AB-04 are given in chapter five table 5.1 and 5.2. ......... 61
Figure 7. 4: Log scale multi-element plot of lithium and associated elements from the world
known lithium brine deposits Garrett (1998); CORFO (1981); Barret and O’Neill
(1970); Anon. (1966); Brown and Beckerman (1990); Tandy and Canfy (1993). The
log scale concentration is ppm. ................................................................................... 64
Figure 7. 5: Combined log scale multi-element plot of Dallol surface brines and hot springs.
The dash line represents Dallol hot springs and the solid lines represent the surface
brines of the Dallol area. ............................................................................................. 64
Figure 7. 6: Bar graph showing the comparisons of lithium contents from different water
bodies with the current research lithium brine content (Figure not to scale). The
lithium values are adjusted by correction factors to allow easy display in the graph.
The vertical dash line is used to split the lithium concentration of different water
bodies in ppb and ppm. ............................................................................................... 66
Figure 7. 7: Scatter plot of Li Vs Rb. ...................................................................................... 67
Figure 7. 8: Generalized Stratigraphic section of the evaporite sequence with the position of
the thin sections micrograph. Thin section micrograph of (P1a & P2a) sylvinite, (P1b
& P2b) upper carnallitite, (P1c & P2c) bischoftite, (P1d & P2d) lower carnallitite,
(P1e & P2e) kainitite and (P1f & P2f) lower halite units. The description of each thin
section micrograph is given in table 7.3. .................................................................... 69
Figure 7. 9: Schematic Model of the Danakil depression for lithium occurrence. .................. 71

List of Tables
Table 3. 1: Description of samples collected from the Dallol and the surrounding area. ........ 20
Table 3. 2: The overall mineral composition members of evaporite sequence, musley area,
Dallol, Ethiopia (Holwerda and Hutchinso, 1968). .................................................... 25

Table 4. 1: Types and origin of lithium deposit (Warren, 2017). The highly concentrated
lithium from hard rock (1.5-4%LiO) is comes from pegmatite related Li deposit (e.g.
Green Bushes, Australia; North Carolina, USA; Bikita, Zimbabwe). ........................ 30
Table 4. 2: The general exploration history of Lithium in Ethiopia and particularly in Danakil
depression (Source: Parsons Company, 1960; GSE and KIGAM, 2012; Tanarmu
Chemical PLC, 2018 (all are open file reports)). ........................................................ 35

Table 5. 1: Geochemical Result of Brine samples (ALS Laboratory service, North Vancouver,
Canada). Samples values described as less than (<) or greater than sign (>) are below
and above the detection limit of the analytical instrument. ........................................ 37
Table 5. 2: Geochemical result of brines samples from Dallol, lake Abijata-Shala and Lake
Chew Bahir (EMPBC lab, Addis Ababa, Ethiopia). Those samples values described
as less than sign (<) and ND shows they are below the detection limit and not
detected by AAS. ........................................................................................................ 40

X
Table 5. 3: Geochemical data of Lithium and other related elements for the MER lakes
(Source: KIGAN and GSE, 2012) and the letter L stands to represent lake. .............. 41
Table 5. 4: Geochemical Results of brine and hot spring samples for their lithium constituents
(Tanarmu Industrial Chemical P.L.C., 2018).............................................................. 42
Table 5. 5: Geochemical result of the rock samples from Dallol area, Danakil depression. The
sign (<) and (>) indicates the ICP-AES limit of detection below and above
respectively for that particular elements and oxides. .................................................. 46

Table 7. 1: Summary of lithium concentration in the known lithium brine deposits of the
world (Source of data: Garrett, 1998; CORFO, 1981; Barret and O’Neill, 1970; Anon,
1966; Brown and Beckerman, 1990; Tandy and Canfy, 1993; Mohr et al., 2010). .... 63
Table 7. 2: Lithium concentration in different water bodies of the world and Comparison with
the current research work. ........................................................................................... 65
Table 7. 3: Description of thin section. .................................................................................... 70

VII
List of Acronyms
AAS Atomic Absorption Spectrometry

ALS Australia Laboratory Service

a.s.l Above mean sea level

b.s.l Below mean sea level

BAC Basal Clastic Unit

BST Bischofitite
°C Degree Celsius

EAR East African Rift system

EMPBC Ethiopian Mineral Petroleum and Biofuel Corporation

3
g/cm Gram per centimeter cube

g/L gram per liter

GPS Geographic Positioning System

GSE Geological Survey of Ethiopia

ICP-AES Inductively Coupled Plasma-Atomic Emission Spectroscopy

IC Ion Chromatography

KIGAM Korea Institute of Geoscience and Mineral Resource Korea

KAI Kainitite

Km Kilometer

LCAR Lower Carnallitite

LHA Lower Halite

Li Lithium

Ma Mega Annum

VIII
MER Main Ethiopian Rift System

MT metric tons

M meter

PPB Parts per billion

PPM Parts per million

SRC Swiss Resource Capital AG

SYL Sylvinite

T tons
UCAR Upper Carnallitite

UHA Upper Halite

USGS United State Geological Survey

UNDP United Nation Development Program

VII
 CHAPTER ONE

1.0 Introduction

1.1 Background
Ethiopia has potential for various types of metallic mineral deposits like gold,
platinum, nickel, copper, iron, chromium, lead, zinc, tantalite and manganese (Tadesse
et al., 2003). The initiatives taken by the government of Ethiopia for the past two
decades increased the metallic and non-metallic mineral exploration activities in the
country (Tadesse, 2009; Getaneh and Tadesse, 2015).

In Ethiopia lithium minerals (lepidolite, spodumene) are found in pegmatite hosted

colombo-tantalite mineral deposits in Kenticha (Tadesse, 2001). No economic
extraction of lithium takes place at the moment; the deposit is only exploited by
surface mining for Niobite/ Tantalite ore minerals.

Yet, not all the possible potential mineral deposits of Ethiopia are systematically
explored due to the expensive nature of exploration and limited number of local
skilled man power. Potential area for required mineral resources can be estimated to
occur is therefore defined using geological, geochemical and geophysical prospecting
methods. Accordingly, this thesis work is focuses on geochemical characterization of
different brine lakes, hot springs and evaporite rock samples to check the presence or
absence of economic potential lithium occurrence in the country.

Now, Ethiopia has vast potential for potash deposits associated with evaporites in the
Danakil depression (Musley area and the surrounding of Dallol) (Muzvondiwa et al.,
2015). The evaporite deposit in the Danakil depression has been extensively explored
for the occurrence of potash. Recently, Circum minerals and Yara Potash obtained
large scale mining licenses for the in situ mining of potash in the area. Thus, the
occurrence of lithium mineral investigation activities have been very limited in and
almost absent in the evaporite rocks of Danakil depression. This is quite evident from
the available literatures, which show the gap very clearly. Though there are some
geochemical studies on brine lakes and hot springs conducted in the southern part of
Danakil compared to northern part (Dallol). There is a serious gap in terms of

1
geochemical investigations of lithium in the Dallol area, due to the extremely difficult
weather conditions, poor infrastructure and security.

Similar to Bradley et al., (2013) description for the occurrence of lithium brine
deposits, the target area is characterized by arid climate condition, closed basin
containing a playa or salar, tectonically driven subsidence, and active volcanic or
geothermal activities. Considering the natural environment for the occurrence of
lithium brine deposit, this thesis aims among other objectives to newly evaluate the
potential of lithium occurrences associated with the potash evaporites and brine
deposit in Ethiopia. The proposed study area is focused on selected area of Main
Ethiopia Rift (MER) lakes, and northern part of Danakil depression. From the MER
lakes it emphasis on lake Abijata, Shala, Abaya, Chamo and Chew Bahir (Fig. 1.1) in
Southern to South Western part of Ethiopia.

Lithium has different application in many industries. It has been applied in glass,
ceramics, metallurgy, air treatment, medicine and recently used for hybrid and
th
electrical car batteries. It becomes the best energy resource of 21 century (Cui et al.,
2016).
Performing this research work is one of manifestations of the effort, intending to
undertake a geochemical investigation for possible lithium occurrence around Dallol
area, northern Afar Depression and some part of the MER lakes. It focuses on the
geochemical variations, hydrothermal activity and comment on the lithium
mineralization potential in the region. This is to provide basic information about the
occurrence of lithium in the area and to help planning future detailed investigation for
this mineral resource.

This research work excludes the pegmatite related lithium deposit of Ethiopia, and it
only emphases on lithium brine and evaporite related deposits.

2
 1.2. Description of the Study Areas

1.2.1 General Location of the study area

The project area extends from Dallol in the north, lake Abijata-Shala to Chew Bahir in
south along the rift valley. The prospect areas are generally located in the Main
Ethiopian Rift System (MER) and northern Danakil depression (Fig. 1.1).
Dallol is located in northern end of the Danakil Depression. It has a latitude and
' " ' "
longitude of 14°14 19 N and 40°17 38 E with an elevation of about 130 meters below
sea level (Fig. 1.1A).

Lake Afdera is located at the southern end of the Danakil depression. It is 220 km far
from Samara and 850 km from Addis Ababa along an asphalted road throughout, and
0 0 0 0
found between latitude 13 11’N and 13 24’N and longitude 40 48’E and 40 56’E in
Afar National Regional State (Fig. 1.1A).

Lake Shala is located in the central MER, some 210 km south of Addis Ababa at grid
0 0
coordinate 7 25’and 38 30’E and has an elevation of 1575 m a.s.l. Lake Abijata is
located north of Lake Shala at 7°38'49"N latitude and 38°37'57" E longitude (Fig.
1.1B).
Lake Chew Bahir is located on the southwestern end of the Southern Nations,
Nationalities and Peoples’ Region, Ethiopia, near the border with Oromia Region. It
0 0
is located at grid coordinate of 4.1-6.3 N and 36.5-38.1 E (Fig. 1.1C).

3
Figure 1. 1: Location map of the lake regions and surrounding of Dallol: A) Danakil
depression (Containing parts of Lake Afdera and Dallol areas part of Circum and
Yara potash license areas); B) Lake Abijata-Shala, and C) Lake Chew Bahir. The Red
Cross indicates the location of the brine samples.

4
 1.2.2 Accessibility
Except lake Chew Bahir, the other study areas (Fig. 1.2) were accessible with good
asphaltic road. The main study area, Dallol is located about 200 to 230 km NE of
Mekelle town, in Afar Region and it is accessible via Mekelle to Agulae town and
then by the road that passes through Berhale town which is under construction (Fig.
1.2).

Figure 1. 2: Accessibility Map of the Study Areas.

1.3 Climate and drainage pattern

According to Garland (1980), the Danakil region is characterized by low precipitation
(below 200 mm/annum) and high average annual temperature ranging from 25 °C to
45 °C 2 (in summer 45 °C to 47 °C) throughout the year. The Danakil Alps and the
Ethiopian Highlands are the water supply area for the Danakil Depression. The rivers
and streams in this area are mostly intermittent. The only perennial river close to the

5
Danakil Depression is the Ragali River. It originates from the western highlands to the
north and west of the potash license area and enters to the Danakil Depression.
Drained areas formed topographic highs and incised valleys, controlled by lithology
and topography. The catchment area for the Danakil Depression bounded by Adigrat
in the west, the Eritrean coast in the north, the topographic highs of the Danakil block
in the east and lake Asale in the south.

The 2012 report of KIGAM and GSE summarizes the background hydrogeology of
the central lake basin, Dofan, Fentale areas and Afdera-Asale sub-basins. It includes
also particular areas explored for lithium and epithermal gold on saline lakes and hot
springs. Several perennial streams start from both sides of the rift margin, enter to the
lakes situated at the low lying middle part of the rift valley, obtaining lake Ziway
(1635m), Langano (1585m), Abjata (1580m), Shalla (1550 m) and Hawasa (1675m).
These different lakes drain by perennial streams such as Meki, Ketar, Bulbula, Hora
kelo, Digo and Tikur Wuha. Moreover innumerable intermitted streams recharge the
lakes after rain fall. In addition, the hot springs surrounded the Lake Shalla, Langano
flows onward the lake.

1.4 Statement of the problem

The study area, Dallol which is located in the Danakil depression is one of the
prospective areas that consist of extensive deposit of evaporite units with
hydrothermal hot springs and surface brines. Meanwhile, the evaporite units in the
surrounding of Dallol which is known by potash deposits, becomes a prospective area
for investigation of evaporite related lithium deposits. Subsequently, there is no study
conducted so far, the present research is intended to study the geology, petrography,
geochemistry of the evaporite horizons for their lithium content. The Ralph M.
Parsons Company did the first exploration for potash in the Dallol area in 1960 and
has made geochemical analysis of evaporite units including lithium but the result was
nil or absence of lithium. However the analytical method they used was not specified.
The KIGAM and GSE, (2012) has made a preliminary investigation for rare metal
occurrence including lithium further south of Dallol and MER lakes. Some of the
lithium result they found from the southern Danakil depression was relatively
enriched than the lithium content of the MER lakes. The exploration work also
recommended the need of further work in the uncovered part of the Danakil

6
depression. Due to the access problem lake Chew Bahir also not covered during their
study. Therefore, this thesis work proposed to fill this gap.

Recently, subsequent to geological mapping, various detail exploration programs like

drilling are being carried in the surrounding of Dallol area for potash deposit by
Circum Minerals and Yara Dallol potash companies and also reserve estimation has
been conducted.

However, study on various aspects for lithium mineralization at the Dallol area is not
yet conducted. Therefore, this thesis work is intended to study the geology and
geochemistry of lithium in the evaporite deposits and brines of the Dallol area and
proposed to fill this gap.

1.5 Objective of the Research

1.5.1 General Objective

The general objective of this research is to conduct geochemical investigation for
lithium occurrence in brines, hot springs and evaporite deposits in Dallol, northern
Danakil depression and some selected MER lakes.

1.5.1.1 Specific objective

 To determine the potential of Li-brines and evaporites depositing lithium
occurrence in Ethiopia (MER lakes and Danakil depression).
 Assessing the lithium potential for further exploration.
 Evaluating the spatial variations of the occurrences among the different
localities.

1.6 Methodology
In order to achieve the aforementioned objectives, several steps were employed. The
research work has been conducted in three phases: Office work, Field work and Post
field approach.

1.6.1 Office Work Approach

1.6.1.1 Secondary Data Collection and Literature Review

Both published and unpublished literatures emphases on brine and evaporite related
lithium deposits in Ethiopia and elsewhere in the world were collected from relevant
companies, institutions and internet source and revised.

7
The desk study was conducted after all the relevant secondary data were collected.
The review part comprises published and unpublished literatures and maps produced
on the occurrence and deposits of lithium in Ethiopia, and in a different place of the
world including the currently most productive Li-mines. Comparison of geological
environment of known global Li-deposits with geological environments found in
Ethiopia, and literature study on the industrial use of lithium was similarly part of the
desk study. In addition, literature studies on the global lithium demand, past, present,
projection for the near future also done.

1.6.2 Field Work Approach

Field investigations of the Dallol area and sampling of the MER lakes were carried
out starting from August 2018. Representative samples were collected for further
geochemical analysis. The primary data collection during the field work was
envisioned to focus on the following target areas:-

The MER lakes: brine sampling has been conducted form lake Abijata-Shala, Abaya,
Chamo and Chew Bahir.

The Dallol area: Core inspection and analysis of the evaporite horizon owned by
Circum and Yara potash companies, and core based geological observation has been
conducted. In addition surface brines and hot spring sampling form mount Dallol and
the surrounding area were accompanied.

Except the geothermal prospect areas, all the other proposed areas were visited and
sampled as much as possible in cooperation with the local industry partners (Abijata-
Shala soda ash, Circum and Yara Potash Companies). During the field work activity
brines, drill cores and surface outcrop rock samples were collected. Field observations
and measurements (such as; GPS locations and description of water and rock samples)
were made with an aim: to verify the analysis result that are summarized during the
literature survey, to fill the available scientific gaps, and to collect additional data
including water samples for further geochemical analysis.

1.6.2.1 Sample collection

Representative brines, hot springs, fresh surface rock samples and drill core rock
samples were collected for major and trace element geochemical analysis.

8
 1.6.2.2 Sampling
Thirty four representative samples (17 rock samples and 17 brines samples) were
collected for geochemical analysis. Due to the limited number of available drill core
samples in the Dallol potash companies, spot samples (not composite samples) from
the quartered core has been taken from the evaporite horizon. Surface out crop of rock
salt samples also taken for analysis. All the brine samples (>1.5 liter) have been
sampled by transparent plastic container and for the case of hot springs color glass
container were used. All the rock samples and seven of the brine samples were
sampled from Dallol and the surrounding area. The remaining brine samples were
collected from lake Chew Bahir (3 samples), Weyto river (1 sample), lake Chamo (1
sample), lake Abaya (1 sample), lake Abijata (3 samples) and lake Shala (1 samples).

1.6.3 Post Field Approach

1.6.3.1 Sample Preparation

Total of 30 samples (17 rocks and 13 brines) were submitted to Australian Laboratory
Services (ALS) in Addis Ababa, Ethiopia. In the ALS lab sample preparation has been
done only for the rock samples. Representative, fresh, and drill core rock salt samples
were dried, cleaned, non-weathered samples were crushed, pulverized, and then sent
to ALS geochemistry laboratory division together with the 13 brines samples to North
Vancouver, Canada for geochemical analysis. The 4 brines samples collected from
lake Abijata-Shala and the duplicate of the 13 brines samples were also again sent to
Ethiopian Mineral, Petroleum and Biofuel Corporation (EMPBC) laboratory at Addis
Ababa, Ethiopia. Because, the detection limit of the ALS geochemistry laboratory
division for lithium is high (10 ppm) and most of the samples have Li concentration
below this detection limit.

1.6.3.2 Analytical Work

After the field investigation, all the selected samples were analyzed for their lithium
and other selected elements. The evaporite rock samples are also analyzed for major
oxides and lithium concentrations.

The analytical work includes:

 Major and trace element laboratory testing for rock samples.

 Drill core samples from potash deposits of Danakil depression are also
analyzed for lithium and major oxides.
9
  Lithium content analysis for selected brine lakes and hot spring samples.

The laboratory examination of brines and hot springs were carried out by such
analytical instrument, Inductively Coupled Plasma-Atomic Emission Spectroscopy
(ICP-AES), Ion Chromatography, and Atomic Absorption Spectrometry (AAS). The
evaporite rock samples (surface out crop and drill cores) were also analyzed for major
oxides and lithium concentration by ICP-AES.

Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) is applied for

analysis of major oxides and lithium content for the collected evaporite rock samples.
The Samples were decomposed by Lithium Metaborate/Lithium Tetraborate
(LiBO2/Li2B4O7) Fusion. A prepared sample (0.100 g) is added to lithium
metaborate/lithium tetraborate flux, mixed well and fused in a furnace at 1000°C. The
resulting melt is then cooled and dissolved in 100 mL of 4% nitric acid/2%
hydrochloric acid. This solution is then analyzed by ICP-AES and the results are
corrected for spectral inter-element interferences. Oxide concentration is calculated
from the determined elemental concentration and the result is reported in that format.
Lithium brine samples are collected, diluted and analyzed directly by inductively
coupled plasma - atomic emission spectrometry (ICP-AES). Further detail on working
principle’s and procedures of ICP-AES and AAS, ICP-AES and ICP-MS, ICP AES
and ICP-OES are given in Aceto et al., (2002); Van de Wiel, (2003) and Fassel and
Kniseley, (1974) respectively.

The determination of halogens and sulfate was done through Ion Chromatography and
sample decomposition was made by potassium hydroxide fusion. A prepared sample
(0.2 g) is fused with potassium hydroxide in a nickel crucible over a flame. The
resulting melt is dissolved in hot E-pure deionized water and topped up to 100 mL.
The solution is subsequently diluted before running on the ion chromatography
instrument, and the detail working procedure is given in Zhang et al., (2012).

1.7 Previous Work and Present Study

Only few previous works has been undertaken in and around the Danakil depression
and MER for occurrence lithium brine and associated evaporite. The Ralph M.
Parsons Company, (1960) did the first exploration in the surrounding of Dallol and
has made detail investigation aiming for potash bearing evaporite deposits for Dallol
potash project. The evaporite samples were collected and analyzed for major and trace

10
elements including lithium, but the result was described as nil or absence of lithium.
However, the analytical method they used is also not specified. Korea Institute of
geoscience and Mineral Resource (KIGAM), Korea and Geological Survey of
Ethiopia (GSE), Ethiopia, (2012), have made reconnaissance survey for lithium and
other elements in saline lakes and hot springs of the Main Ethiopian Rift lakes and
some part of the southern Danakil depression. The lithium concentration from brines
of the Danakil depression were enriched in their lithium content 4.62 and 6.2 ppm in
lake Asale and lake Afdera respectively, and it is the highest value compared with the
MER lakes. The KIGAM and GSE (2012) also recommended the need of further
exploration work in parts of the previously studied areas and uncovered part of the
Danakil depression due to the elevated lithium values. During their investigation,
mount Dallol and the surrounding potash deposit area were also not covered and
analyzed for lithium. Currently, various detail exploration programs like drillings are
undergoing in the surrounding of Dallol area for the purpose of evaluating the potash
deposits.
Based on the study conducted by KIGAM and GSE (2012) and few other data
generated so far for the Danakil lithium brine occurrence, the present study is directed
towards understanding the lithium distribution and variation in brines and evaporites
in the area. As a result, this thesis work is aiming to examine the potential lithium
occurrence from the Dallol hot springs, the surrounding surface brines and the potash
bearing salt deposits. In addition it covers lake Afdera in southern part of Danakil
depression and some selected MER lakes like lake Abijata-Shala, and lake Chew
Bahir.

1.8. Thesis Structure

The thesis is structured in eight chapters. Chapter one gives general information about
the study area, the purpose and methods followed in the research. Second chapter
provide a regional scale overview. Chapter three gives detail descriptions about the
geology of the Dallol area. Chapter four deals about the general overview of lithium
as well as its property and deposit types. In chapter five primary and secondary
geochemical data are presented. Chapter six is focused about the extraction techniques
of lithium brines. Chapter seven gives emphasis on the discussion and comparison of
the current work with the previous researches conducted. Ultimately, the main
conclusion and recommendation for the future study is dealt in chapter eight.

11
 CHAPTER TWO

2. Regional Geological Setting and Rift Basins

2.1 Main Ethiopian Rift System (MER)

The Main Ethiopian Rift (MER) and the Afar depression represent the northern
portion of the East African Rift System, among others, (Woldegabriel et al., 1990;
Corti et al, 2009; Kurkura et al, 2009; Rooney et al, 2010; Abbate et al, 2015;
Hutchison, 2016). The Ethiopian Rift extends more than 1000 km in a NE-SW to N-S
direction from the Afar depression southwards to the Turkana depression (Tadesse et
al., 2018), and wide’s in average ~80 km (Mohr, 1983b). The extensional deformation
of the MER started to develop in the late Oligocene-early Miocene (Ebinger et al.,
2000; Bonini et al., 2005; Wolfenden et al., 2004).

The MER divided in to Southern, Central, and Northern sectors (Fig. 2.1A), and ages
of volcanism advances northward in the rifting development (Bonini et al, 2005;
Corti, 2009). The development of MER show dissimilar ages in different segments
suggesting diachronic opening of the EARS (Ayalew et al., 2018). Continental rifting
began in the southern segment of the MER (~15-18 Ma) (Woldegabriel et al., 1990)
and in the northern MER (~11-10 Ma) (Wolfenden et al., 2004). The rift volcanic
rocks are characterized by bimodal composition (basalt to rhyolite) with minor
intermediate composition (Ayalew, 2000). The origin of this bimodal distribution is
still debated (Rooney, 2010; Rooney et al., 2011; Rooney et al., 2007; Rooney et al.,
2014; Hutchison et al., 2016).

Kurkura et al (2009) stated that the Ethiopian volcanic region was dominated by basic
volcanic rocks, and minor felsic rocks. However, According to Mohr (1992) the
proportion of felsic products in the Main Ethiopian Rift Valley is high, exceeds 90%
of the total volume of the rocks. The existences of these dominated felsic igneous
rocks are supposed to be the potential source of Lithium in the MER, which is the
main motive for this thesis work.

The Northern MER is characterized by bimodal eruption in which the felsic volcanic
products mainly rhyolite dominate the basic volcanic products (Cortti, 2009 and
reference therein). In the northern MER exposure of the early eruption of flood basalts
was followed by the eruption of Mid-Miocene from the shield volcanoes in the rift

12
shoulders (Chernet et al., 1998). Trachytic flow (10.5 ma) from Megezez volcano and
the base of Adama basin in the Kesem formation is known by the sequence of basalts
and ignimbrites (~10.5 ma) and the top part of the rift basin is manifested by
extensive ignimbrite units (~6.6 ma) (Wolfenden et al., 2004). Quaternary bimodal
volcanic activity (lava, pyroclastic and volcanoclastic strata (Wonji Group) are
recognized in the northern part of MER (Woldegabriel et al., 1990 and references
therein). Different scholars describe the volcanic hiatus of the northern MER among
others, Chernet et al., 1998; Wolfenden, 2004.

The central MER is well documented and characterized by the eruption of localized
old flood basalts (~30 Ma) followed by intermediate and acidic rocks ( ~17-12 Ma)
(Woldegabriel et al., 1990); as well as eruption of Late Miocene (~11-8 Ma) basalts
and trachybasalts (Woldegabriel et al., 1990; Bonini et al., 2005).

The Tertiary volcanic activity in the Southern MER started since the pre-rift flood-
basalt event and dated ~ 45 Ma (Ebinger et al., 1993; Woldegabriel et al., 1999;
Ebinger et al., 2000). The geology of the Main Ethiopia Rift has been treated and
reviewed, among others, by Corti (2009); Woldegabriel and others (1999) and Abbate
et al., (2015).

The central part of the Danakil depression is covered by recent volcanic and
sedimentary rock units (Fig. 2.1B). The western escarpment of the Danakil depression
is known by the exposure of Neoproterozoic basement rocks, Mesozoic sedimentary
rocks and Eocene-Miocene basalts.

13
Figure 2. 1: Digital elevation model (SRTM data) of the Main Ethiopian Rift
showing the main rift segments (Corti, 2009): (from north to south) Southern Afar (S-
Afar), Northern Main Ethiopian Rift (NMER), Central Main Ethiopian Rift (CMER)
and Southern Main Ethiopian Rift (SMER). BRZ: Broadly Rifted Zone; CB: Chew
Bahir Rift; GB: Gofa Basin and Range. B) Simplified geological map of Ethiopia
(Abbate et al., 2015; http://www.gse.gov.et/index.php/2016/09/03/overview-3/).

2.2 Afar Depression

The triangular-shaped Afar Depression (Fig. 2.2A) covers an area of approximately
2
200,000 km and is bounded by the Ethiopian Plateau in the west and the Somalia
Plateau to the southeast, the Ali-Sabieh and Danakil Blocks in the eastern and
northeastern sides of the Afar Depression (Beyene and Abdelsalam, 2005).The
Danakil depression is the northern part of the Afar Depression. It is result from the
presence of tectonic triple junction where the Red Sea and Gulf of Aden gradually
become visible on land and it is one of the most volcano-tectonically active parts of
the East African Rift system (EAR) which is dominated by basaltic to rhyolitic
magmatism (Beyene and Abdelsalam, 2005; Aerts et al., 2006; Corti, 2009; Abbate et
al., 1995; Abbate et al., 2015; Hagos et al., 2015).

According to Varet, (1978), the geological units of the Afar Depression and marginal
areas (Fig. 2.2B) can be divided into four broad groups (a) Neoproterozoic basement,
Mesozoic sedimentary rocks, and Eocene Miocene basalts; (b) Miocene igneous
rocks; (c) Pliocene volcanic rocks; and (d) Quaternary volcanic and sedimentary
rocks.
The regional geological setting of the Dallol, the first and the main target area of this
research work, is the northern extension of the Danakil depression is well-defined via

14
Solomon and others, (2011); Davidson et al., (1994); Drury et al., (1994); Holwerda
and Hutchinson, (1968). The western part of the Danakil depression is covered by pre-
rift groups (Neoproterozoic basement rocks, Mesozoic sedimentary rocks and Eocene-
Miocene basalts). The Neoproterozoic basement represents part of the Arabian-
Nubian Shield, and western margin of the Afar Depression (Solomon and others,
2011; Beyene and Abdelsalam, 2005). The center of the Danakil depression mainly
covered by young Quaternary sediments and volcanic rocks.

Direct field visit and previous work by Holwerda and Hutchinson (1968) show up the
evidence of volcanic activity in the Danakil depression. These are active volcanic
peaks (south of Lake Asale), basalts intercalated with evaporite beds (east of the salt
pan), recent cinder cones (in the same area), the phreatic explosion (at Black
mountain), circular, crater-like features (east of the Circum camp site) at Dallol, and
Black mountain.

Darrah et al., (2012) states that, brine fluids existed in the Dallol area are extremely
salty (>500g/L), highly acidic, and gas-rich. Lake Afdera that found in the Danakil
depression is a saline body of water fed by hydrothermal springs (Enrico et al., 2017).
The salt dome fluids and hot springs are assumed to result from the interaction
between hot mantle fluids or basalt dyke injections with evaporite deposits at
unknown depths. The Danakil depression is a Tertiary rift basin filled with evaporites
similar the outcrops nearby the Dallol Mountains (St. Jhon, 2016). The salt dome
fluids and hot springs are assumed to result from the interaction between hot mantle
fluids with evaporite deposits at unknown depths. Darrah et al., (2012) states that,
brine fluids existed in the Dallol area are extremely salty, highly acidic, and gas-rich.
Lake Afdera that found in the Danakil depression is a saline body of water fed by
hydrothermal springs (Bonatti et al., 2017).

15
Figure 2. 2: A) Location of the Afar depression and local fault lines in the map of
East Africa showing some of the historically active volcanoes (red triangles) and the
Afar Triangle. The red triangles show historically active volcanoes (Source: USGS,
1999,http://pubs.usgs.gov/gip/dynamic/East_Africa.html). B) Simplified geologic
map of the Afar depression (Beyene and Abdelsalam, 2005).

16
 CHAPTER THREE

3.0 Geology of the Study Areas

3.1. Chew Bahir Basin

One of the prospect area, Chew Bahir basin (Fig. 3.1) part of the southern Main
Ethiopian Rift, located in a ~250 to 300 km extensive rift zone, and bounded by the
Omo-Turkana basin to the west and the southern sector of MER to the east ( Ebinger
et al., 2000; Foerster et al., 2012; Foerster et al., 2014). Its rift setting and the
surrounding geological units are best described in Ebinger et al., (2000); Corti,
(2009); Davidson, (1983) and Foerster et al., (2012).

The western boundary of Chew Bahir basin, the Hammar range, consists of
Precambrian basement of undifferentiated gneisses; and the eastern border of the
basin which is the escarpment of the Teltele-Konso range, was known by the
exposures of Miocene basalts and trachytic centers (Davidson, 1983 and Foerster et
al., 2012). The central part of the Chew Bahr basin is filled with different fluvitile,
alluvial, lacustrine and undifferentiated sediments.

Figure 3. 1: Geological map for the catchment of the lake Chew Bahir (Foerster et al.,
2012 and reference therein).

17
 3.2 Zeway-Shala Basin
It is the second prospect region under this thesis work. The Zeway-Shala basin,
containing lake Abijata-Shala, is a closed drainage system found in the central
segment of the Main Ethiopian Rift. The structural trend of the rift and the adjacent
topographic features are well described through Benvenuti et al., (2002); Bonini et al.,
(2005); Menard et al., (2014). The major lithological units (Fig. 3.2) exposed in Shalla
area are rhyolites associated with ignimbrites and pumice breccias with minor basalts.
In addition, the boarder of the lake region has an exposure of Early to Middle
Holocene deposits of colluvial, fluvio-deltaic and lacustrine gravels, sands, muds,
lacustrine diatomite’s and volcanoclastic deposits (Benvenuti et al., 2002).

The geology of the basin is best treated by different scholars among others by
Benvenuti et al., (2002); KIGAM and GSE (2012), open file report. The ignimbrites
unit surrounding the lake regions is intersected by several NNE-SSW trending faults
of the Wonji Fault Belt (UNDP, 1973).

Figure 3. 2: Simplified geological map of the Lakes Region in the CMER (Adapted
from Benvenuti and Carnicelli, 2015). The details and main characteristics of each
Synthem are described by Benvenuti et al., (2002) and Benvenuti and Carnicelli,
(2015).

18
 3.3 Geology of the Danakil area
The first and main study area Dallol lies in the northern part of the Afar depression or
Danakil depression (Chapter 1: Fig. 1.1A). The general geological units (Fig. 3.3) of
the area from West to East is characterized by: (1) Neoproterozoic metavolcanic and
metasedimentary rocks, (2) gently dipping Quaternary alluvial deposits, (3)
evaporites, which consists of salt deposits (halite and potash), and (4) salt and mud
deposits on the salt flat and sulfur deposit especially on mount Dallol and its
localities. The detail description of the samples located on the geological map is given
in table 3.1.

Figure 3. 3: Simplified Geological Map of the northern Danakil area (Adapted from
Solomon and others, 2011). The green triangle represents the location of surface out
crop rock salt samples; the red crosses indicates the location of brines and hot springs
and the light blue star represents the location of the Drill holes. Descriptions of the
samples located on the geological map are given in table 3.1.

19
Table 3. 1: Description of samples collected from the Dallol and the surrounding
area.

Sample ID Sample Description

Type
RD-02 Evaporites CTMS (Carnalite Type mixed Salt which is a mixture
from test of Sylvite + UCAR)
ponds
RD-01 Evaporite Kainite 1'st Phase
rocks from
test ponds
CR 9 (RD- Evaporite Rock salt samples from the last stage of the test
03) rocks from solution mining pond of CIRCUM fly camp
test ponds
RD-04 Evaporite Halite samples from the salt flat of Dallol Depression
rocks from
salt flat
DH 1 & DH Water Hot spring samples taken from Dallol mountains.
2 Active hot spring with variable temprature.
YD-1A Water Brine Sample from the part of the ground water
system and it is found in the center of the salt falt as a
pond
YD-2A Water Brine sample from the salt flat at the foot of mountain
Dallol as a pond
DL-1B Water Brine sample close to the road as a pond in the way
between Circum fly camp and their Permanent camp
site
DL-2A Water Brine samples close to the Circum fly camp as a small
lake (Pond)
DL-3A Water Brine Samples on the gravel road as a small pond
between fly camp the Circum camp site

The field investigation shows part of the western escarpment with metavolcanics and
metasedimentary units, alluvial fan deposits and transition zone (mud and silt
mixture) (Fig. 3.4A). The area adjacent to the alluvial fan deposits is dominated by the
presence of salt and mud mixtures, which form a transition zone on the western
margins of the evaporite zone (Fig. 3.4A). The muds are mainly sandy at the west and
become clay towards east.

East of the transition zone and west of mount Dallol is characterized by the exposure
of the upper most and the recent salt deposits (Fig. 3.4B). In the center of the salt flat
the part of the ground water system is exposed in the surface and brine samples were
taken for geochemical analysis (Fig. 3.4C).

20
Mount Dallol is manifested by the occurrence of sulfur, mud, salt deposits (Fig. 3.4D
and Fig. 3.4G). The occurrence of sulfur is commonly dominant on the mount Dallol
and its vicinities giving a rotten-egg smell to the area. On top of the mount Dallol
(Fig. 3.4D), active hot springs with variable temperature are being erupted and
forming semi-circular to circular shaped ponds.

Small and continuous circular collapsed land forms are localized in the center of the
salt flat and these collapsed structures are almost parallel to the main rift axis of the
Danakil depression. Some of these collapsed structures are filled with waters (Fig.
3.4E) and the other are being dried (Fig. 3.4F). Other topographic features observed in
northern part of the Danakil depression is elevated and circular depression (Fig. 3.4H)
of crater like features on the center of the salt flat and is located close to the Ethio-
Eritrea boarder.

Figure 3. 4: Field photographs showing part of the Dallol and the surrounding area.
(A) Part of the western escarpment, alluvial fan and transition zone, (B) Salt flat, (C)
Part of the ground water system in the salt flat, (D) Hot spring with sulfur occurrence
at the top of mount Dallol, (E) Pond in the transition zone, (F) Circular depression in
the salt flat, (G) Side of Black mountain with gypsum, halite, silt and clay deposits
and (H) Elevated circular depression.

21
According to Holwerda and Hutchinso, (1968), the Danakil evaporite are young
(Quaternary) in age and the evaporation sequences are deposited during the Neogene
time (2.5 ma to the present), and the overlaying sediments are Marls, gypsum,
anhydrites and clays.

The Danakil Depression (parts of Ethiopia and Eritrea) is an area of extreme

hydrothermal activity with potash occurrences related to rift magmatism, marine
flooding, and deep brine cycling. The Dallol is the northern part of the Afar
depression and runs SSE parallel to the Red Sea coast but is some 50-80 km inland
and separated from the sea by the Danakil Mountains. It is 185 km long, up to 70 km
wide.

3.3.1 Drill-Core Based Geology of the Danakil Evaporite units

The evaporite sequence in Danakil depression riches in thickness about 970m
(Warren, 2016). The overall evaporite sequence (Drill Core Based Geology) from top
to bottom is the overburden, upper halite, marker bed, sylvinite unit, upper
carnallitite, bischofitite, lower carnallitite, kainitite, lower halite and basal clastic unit
at the bottom. Different scholars like Holwerda and Hutchinson, (1968); Muzvondiwa
et al., (2015); and Warren, (2016) describe the core based local geology and the
minerals assemblage (Table 3.2) of each lithology’s for the Danakil potash deposit.
The evaporite sequence is overlain by clastic Overburden, which is a poorly sorted
sequence of clay (mostly iron-rich), sand, gravel and gypsum as well as lenses of
coarsely crystalline Halite. Gravel-rich layers can occur with some angular rock
fragments. The contact with the underlying Upper Halite unit is gradational and it
ranges from 49.2 m to 296.5 m and averages 164.61 m in thickness (Fig. 3.5).

The uppermost unit in the evaporite sequence is the Upper Halite Unit (UHA),
which consists of a mostly translucent, coarsely crystalline, massive, Halite-rich rock
salt with scattered intercalations of Anhydrite, narrow interlayers of clay and
mudstone and rare gypsum partings. The thickness ranges from 17 m to 150.2 m (Fig.
3.5).

22
Figure 3. 5: The Generalized Stratigraphic Section of the Potash Bearing Evaporite
Deposit of Circum and Yara Potash License Areas.
The Marker Bed is an important indicator of the closeness of the underlying potash
horizons. It is characterized by mostly halite-rich rocks which are interbedded with
finely crystalline anhydrite and minor clay, gypsum and Sylvite. In some drill holes,
massive anhydrite-rich rocks occur with lesser halite content. The thickness ranges
from 1.2 m to 15.1 m (Fig. 3.5).

23
The Sylvinite Unit (SYL) is composed of fine-grained Sylvite-rich rock with Halite
and Anhydrite. This mostly translucent to opaque unit occurs in some cases with
appreciable amounts of Carnallite, Kainite and banded Kieserite (Chapter 7: Fig. 7.8:
P1a & P2a). The contact with the underlying Carnallite unit is generally sharp and it
ranges from 1.2 m to 10.4 m in thickness.

The Upper Carnallitite Unit (UCAR), which is characterized by a finely crystalline,

massive Carnallite with finely crystalline interbedded Kieserite and Halite, in addition
finely crystalline, interbedded, gently dipping Sylvite, Anhydrite and Kainite (Chapter
7: Fig. 7.8: P1b & P2b). The contact with the underlying unit is very sharp. It ranges
from nonexistent to a maximum thickness of 14.6 m (Fig. 3.5).

The lower carnallitite unit is overlain by the Bischofitite Unit (BST), which is a
whitish, finely crystalline rock with intercalations of colorless, finely crystalline
Bischofite and irregular interbedded Carnallite. In general it is dominated by halite
crystals with finely distributed bischofites (Chapter 7: Fig. 7.8: P1c & P2c). Within
this unit, flat-dipping Kieserite and Sylvite laminations can occur. The Bischofitite
unit is locally absent in the potash property area and, where present, its minimum
thickness is about 4.6 m and maximum thickness is about 84.3 m (Fig. 3.5). It is not
considered to be part of the deposit. In general, this unit is dominated by Bischofite
(up to 80 %) with intercalations of Carnallite and Sylvite.

The Lower Carnallitite Unit (LCAR) overlies the Kainitite and consists of a
variable sequence of finely crystalline Carnallite and Kainite, lesser Sylvite and rare
narrow interlayers of clay. It is translucent to light yellowish and weakly bedded. It is
characterized by typical fine and coarse grain layering of Carnallite and halite crystals
which shows a fraction of sedimentary banding (Chapter 7: Fig. 7.8: P1d & P2d). The
contact with the underlying Kainitite unit is gradational. The Lower Carnallitite Unit
ranges from 1.2 m to 16.2 m in thickness (Fig 3.5).

The Kainitite Unit (KAI) is mostly massive, finely crystalline Kainite with Halite
and appears thin-bedded and flat-dipping with narrow partings and interlayers of clay
(Chapter 7: Fig. 7.8: P1e & P2e). Locally, the Kainitite is interbedded with Carnallite.
The minimum thickness of the Kainitite encountered in drilling is 0.8 m; the
maximum thickness is 15.0 m (Fig. 3.5).

24
The Lower Halite Unit (LHA) is a sequence of finely crystalline Halite-rich rock salt
with thin interbedded layers of Anhydrite, mudstone and sometimes clay. It shows
perfect zoned cube of halite crystals with huge fluid inclusion (Chapter 7: Fig. 7.8:
P1f & P2f). The Lower Halite Unit has a maximum thickness of about 46 m and
averages about 19 m in thickness (Fig. 3.5).

The evaporite rocks in the Dallol Potash deposit area are underlain by a Basal
Clastic Unit (BAC), which can be described as an unevenly sorted set of clastic
sediments consisting of mudstone and sandstone. The boundary between these clastic
rocks and the overlying crystalline rock salt is abrupt.

Table 3. 2: The overall mineral composition members of evaporite sequence, musley

area, Dallol, Ethiopia (Holwerda and Hutchinso, 1968).

Member Average Mineralogical CompositionalVariations within

Composition (Percent in brackets)
Marker Halite, NaCl, (85-90)
Beds Anhydrite, CaSO4,(15-10)
(Younger
Halite)
Sylvite Halite, NaCl, (50)
Sylvite, KC1, (35-40)
Anhydrite, CaSO4, (15-10)
Intermediate Halite, NaCl, (33)
Carnallite, KCl. MgCL2.6H20, halite, carnallite, anhydrite,
(20)
Anhydrite, CaSO4,(15)
Kieserite, MgSO4.H20, (10)
Sylvite, KCl, (10)
Kainite, MgSO4.KC1.3H20, (10)
Polyhalite,
2CaSO.MgSO4.K2SO4.2H20 (2)
Bischofite,MgCl.6H2O
Kainite Kainite, MgSO4.KCl. 3H2O, (70)
Halite, NaC1, (30)
members
Anhydrite more abundant as
seams at base, upward becomes
disseminated and decreases
Composition variable laterally
into barren halite or anhydrite-rich
evaporite, anhydrite as seams
Sylvite more abundant at top
kieserite, prevalent throughout
kainite more abundant at base
Kainite greatly predominates at
top, halite increases toward base

25
The Danakil Potash Deposit contains three main potash bearing minerals: Sylvite
(KCl), Carnallite (KMgCl3) and Kainite (KMg(SO4 x 6 H2O)Cl x 2.75 H2O). The
evaluation of lithium content on this work targeted on those potash bearing evaporite
deposits, to use the lithium as a bi-product for the potash company.

The stratigraphic section (Fig. 3.6) of the evaporite horizons in the Danakil depression
prepared by different scholars are presented for comparison. The core based geology
of the evaporite deposits in the Danakil is well described in Muzvondiwa et al.,
(2015), and the intermediate members are detail mapped as Upper carnallitite
(UCAR), Bischofitite (BST) and Lower Carnallitite (LCAR) units. In addition, below
the lower halite unit it is logged as basal clastic, which is unevenly sorted set of
clastic sediments consisting of mudstone and sandstone.

Figure 3. 6: The Generalized Stratigraphic Section of the Potash Bearing Evaporite

Deposit of the Danakil depression of Musley area, Dallol, Ethiopia and part of the
Circum and Yara Potash License Areas (Holwerda and Hutchinso, 1968;
Muzvondiwa et al, 2015; Warren, 2016).

26
 CHAPTER FOUR

4.0 General Information and Background Description on

Lithium

4.1. Introduction
Lithium is located at the top of the periodic table, with an atomic number and weight
of 3 and 6.9 respectively, is soft, and a silvery-white color (Krebs, 2006; Warren,
2017). It has the lowest melting points (180 °C), highest melting and boiling points of
the alkali metals (Lide, 2005). Lithium has a very low density (0.534 g/cm3), and it
can float on hydrocarbon oils and is one of the three metals that can float on water, the
other two are sodium and potassium. It is found in a number of minerals like
spodumene, petilite, lepidolite, and amblygonite. All those minerals are silicates
associated with pegmatitic intrusions. In addition lithium is also commonly associated
in the form of lithium carbonate with potash in evaporite deposits (salt lakes).
Estimates of the average background value or crustal abundance of lithium vary in
different rocks, however it is likely to be approximately 17-20 parts per million
(ppm). In igneous rocks, the abundance is typically 28-30 ppm, but in sedimentary
rocks, it can be as high as 53-60 ppm (Evans, 2014; Kunasz, 2006). Generally, its
concentration or crustal abundance is approximately 20ppm.

4.2 Genesis of Lithium

4.2.1 Occurrence and Source of Lithium

The highly reactive nature of lithium makes its geochemistry complex and interesting.
Lithium-minerals are formed in magmatic processes, and it crystallizes at the last
stage of crystallization. At present, many lithium-containing minerals are known, but
few of them contain high concentrations, and it can also be found in naturally
occurring salt solutions as brines in dry salt lake environments (Vikstrom, 2013).
Source of lithium can be from primary or secondary. The primary source for lithium
is extracted from pegmatite deposits, brines, evaporite, and deep ground water bodies
(oil or gas deposit, formation water and geothermal water). The secondary source of
lithium is from recycling of Li-bearing products. Currently, the challenges for this
recycling are low concentration of Li in the products and absence of systematic
logistics collection. Recycling of lithium is minor but has increased gradually owing
to the growth in consumption of lithium batteries. One domestic company has
27
recycled lithium metal and lithium-ion batteries since 1992 in British Columbia,
Canada (Jaskula, 2018). In 2015, the newly constructed company began operating the
first United State recycling facility for lithium-ion vehicle batteries in Lancaster, OH
(Jaskula, 2019).

4.2.2 Types of Lithium Deposits

Lithium deposits in the world are of generally three main types: brines and related
evaporites, pegmatite, and sedimentary rocks (Table 4.1). Brines containing lithium
make up 66% of the world’s lithium resource, pegmatite make up 26%, and
sedimentary rocks make up 8% (Gruber et al., 2011).

4.2.2.1 Brines and Evaporite Deposits

Brines are saline waters with high contents of dissolved salts, and the best common
environment for lithium bearing brines are lacustrine (lake), playas (salt flats), and in
some such playas site, evaporation has deposited layers of salts, commonly halite
(NaCl). Lithium is thought to have been derived from erosion of rocks surrounding
the playas and from hot springs that feed water into the playas (Ide and Kunasz, 1989;
Kesler, 1994). This study did not cover the rocks that surrounding the lakes. Currently
the top leading countries that contain the highest concentrations of lithium deposit and
dominant lithium brine extraction are in Chile, Argentina, China, and Tibet (Fig.4.1).

Evaporite deposits are formed by the precipitation of salts when water loss
(evaporation) exceeds the water gain (recharge) in to the basin (Lee et al., 2010). The
Li-brine deposits get nowadays more attention, because they are more competitive
and form the better alternative compared to hard rock mining. They have a lower
environmental impact and are less expensive and more cost effective to exploit
(Warren, 2010; Lee et al., 2010). All closed-basin lithium-brine deposits that are of
present economic interest are Quaternary in age, and basins that contain lithium-
enriched brines have a number of different tectonic origins.

Lithium brine deposits (Table 4.1) are subdivided in to continental (majority of the
global lithium resource), geothermal (~ 3% of the global lithium resources) and
oil field deposits (~3% of known global lithium resources) (Amanda, 2018).
Continental lithium brine deposits accounts about three-fourth of the current world
lithium production (Warren, 2017).

28
Figure 4. 1: (A) World map of lithium brine deposits with inset showing. (B) detail in
South America. (C) Histogram showing the bimodal latitudinal distribution of Li-
brine deposit in northern and southern arid belts (Adapted from Bradley et al., 2013).

29
Table 4. 1: Types and origin of lithium deposit (Warren, 2017). The highly
concentrated lithium from hard rock (1.5-4%LiO) is comes from pegmatite related Li
deposit (e.g. Green Bushes, Australia; North Carolina, USA; Bikita, Zimbabwe).

Type of Source Description Grade Examples

Deposit
Magmatic Coarse grained igneous rock 1.5-4%LiO Green Bushes,
Fluid formed during late stage Australia,
Pegmatit crystallization of magma North
es Carolina, USA;
Bikita,
Zimbabwe
Saline Lenses of saline lacustrine 0.4%LiO Kings Valley,
Hectorit Brine smectite clay in association Navada, USA;
e with volcanic centers Sonora,
Mexico
Saline Hydrothermally altered 1.5%LiO Jadar, Serbia
Brine boro-silicates in sediments
Jadarite
of an enclosed saline
lacustrine basin
Saline Salt pans or salars in 0.04- Clayton
Brine enclosed basins with lithium 0.15%Li Valley, USA;
enrichment likely to be from Salar De
Contine hotsprings Atacama,
ntal Chile; Salar de
hombre
muerto,
Argentina
Saline Elevated level of lithium 0.01- Salton Sea,
Geother
Hydrother contained in steam at 0.035%Li California,
mal
mal Brine geothermal power station USA
Basinal Elevated level of lithium 0.01- Smackover
Saline contained in waters or 005%Li oilfield,
Brine brines produced in oilfields Arkansas,
Oilfield
USA;
Foxcreek,
Canada

4.2.2.2 Sedimentary Rocks

Lithium is also found in sedimentary rocks, including clay and lacustrine evaporites.
In the clay deposits, lithium is a constituent of clay minerals, such as smectite, from
which it must be separated by processing. Hectorite, [(Mg,Li)3Si4O10(OH)], is a type
of smectite that is rich in magnesium and lithium. The best known hectorite deposit
(containing 0.7% Li) is in Hector, California, and the lithium-bearing hectorite is used
for cosmetic and other applications (Garrett, 2004).

30
 4.2.2.3 Pegmatite
Pegmatite deposits are coarse-grained intrusive igneous rocks that formed from the
crystallization of magma at certain depth in the crust. Lithium in pegmatite (Fig. 4.2)
is widely distributed, and it usually present in pegmatite in the form of mineral
spodumene (LiAlSi 2O6), petalite (LiAlSi4O), lepidolite
[(KLi2Al(Al,Si)3O10(F,OH)210], amblygonite [(Li,Na)AlPO (F,OH)], and eucryptite
(LiAlSiO4)4) (Tahil, 2008).

Figure 4. 2: World map showing the locations of lithium-cesium-tantalum (LCT)

pegmatite deposits or districts, including smaller districts in the United States. The
symbols are color-coded by age. Huge deposits are represented by larger symbols
(Bradley and McCauley 2016; Bradley et al., 2017).

4.3 Economic Concentrations of Lithium in mineral deposits

Economic concentrations of lithium brine deposit range from 200 to 4,000 parts per
million (ppm) (Gruber et al., 2011; Kesler et al., 2012; Jephcott, 2016). But, currently
low lithium concentration well below the lithium brine cut-off grade 200 ppm
(Bradley et al., 2013) also extracted as a byproduct (e.g. Dead Sea brine 12-23 ppm
(Tandy and Canfy, 1993); Great Salt Lake 18-40 ppm (Mohr et al., 2010)). Among
the current active economical extractable lithium brine deposit the concentration of
lithium was noted as 0.0146% in Smackover formation in the Gulf Coast region of the
United States (Mohr et al., 2010) and 1400 ppm (or 7000 ppm) of lithium in Salar de

31
Atacama, northern Chile (CORFO, 1981; Garrett, 1998). The pegmatite deposit
ranges from 0.59% Li in Jiajika, China; 1.59% (~2%) Li in Greenbushes, Australia
(Gruber and Medina, 2010).

4.4 World Lithium Production, Consumption and Demand

Forecast
Lithium production was raised in the world by an estimated 12% in 2016 in response
to increased lithium demand for battery applications, and continuing exploration
indicates the resources have increased more than 53 million tons (Jaskula, 2018).
Likewise, lithium production was increased in 2017 - 2018 from 69,000 t to 85,000 t,
which is increased by 23% in response to high lithium demand for battery
applications (Jaskula, 2019).

Global annual lithium consumption increased by over 6% annually between 2000 and
2008, rising from 13,375 to 21,280 t (or 113,270 t of lithium carbonate). An increase
of around 300,000 t in the demand for lithium carbonate is forecast in 2020
(GENIVAR, 2013).

Global future lithium demand is expected to raise with an annual growth rate of over
10% in the next ten years, and currently, the top four lithium-demanding markets are
battery, glass, ceramics and lubricating greases, and the battery industry is currently
the biggest lithium-demanding market (Cui et al., 2016). According to Jaskula, (2019)
the battery industries has taken the highest portion (56%) of world end user market of
lithium. The current top lithium brine suppliers for the world lithium market are
Argentina, Chile, Australia and China (Warren, 2017; Cui, et al., 2016; Jaskula,
2019).

Economic considerations: The profit margin for mining companies in the lithium
business lies around 46% (Lithium Report 2016 by Swiss Resource Capital (SRC)
AG).

4.5 General Condition for the formation of Lithium Brine Deposits

and the Situation in Ethiopia

Lithium brine deposits are accumulations of saline ground water that are enriched in
dissolved lithium, and the word brine refers to a solution of salt (sodium-chloride) in
water. Lithium brine deposits are volcanic in origin and are often found situated in
32
desert locations such as Argentina, Bolivia, Chile and China (Bradley et al., 2013).
The favorable conditions for the formation of all lithium brine deposits in the world
(Fig. 4.3) with common characteristics include: arid climate condition, closed basin
containing a playa or salar, tectonically driven subsidence, associated igneous or
geothermal activity, suitable lithium source-rocks, one or more adequate aquifers, and
sufficient time to concentrate brine (Bradley et al., 2013).

Figure 4. 3: USGS Schematic deposit model for lithium brines deposit showing part
of a closed-basin system consisting of interconnected sub-basins. The sub-basin
containing the salar is the lowest (Bradley et al., 2013).
All the geologic and temperature condition, (as Bradley et al., (2013): arid climate
condition, closed basin containing a playa or salar, tectonically driven subsidence,
associated igneous or geothermal activity, suitable lithium source-rocks, one or more
adequate aquifers, and sufficient time to concentrate brine), for the formation of
lithium brine deposit mentioned in USGS model shares number of common similar
characteristics with the MER and Afar depression. Based on the above brine
indication, this work has focused on the brines and evaporite deposits of the Danakil
depression for potential formation of lithium. The conditions of the USGS model for
the formation of lithium look active in the Danakil depression (Fig. 7.8).

33
The Afar depression in general is assumed to be the main interesting area for the
possible potential area of evaporite or brine related lithium occurrences. The
geological setting and climatic condition in this project area is favorable for the
formation of evaporate deposit, and the evaporation is much higher than precipitation.

The Afar Depression is a challenging area for search of mineral resource due to hard
climate condition which includes the Danakil Desert and the lowest point in the
world. Dallol, Ethiopia is also part of the Depression, one of the hottest places year
round anywhere on the Earth.

4.8 Prior Work on Lithium-Brine Deposits Exploration of

Ethiopia
Limited knowledge existed on the occurrence of lithium brine and associated
evaporite deposit of Ethiopia (Table 4.2). The Ralph M. Parsons Company (1960) and
KIGAM and GSE (2012) were the only work existed in the country before 2012 to
analyze the lithium in Danakil evaporite units and hot springs. The Ralph M. Parsons
Company (1960) was conducted a survey in the Danakil depression of Ethiopia and
part of Eritrea mainly aiming for potash, sulfur and other minerals. The company
conducted geochemical analysis for potash bearing minerals and also analyze for
lithium but the result was Nil (Zero). The type of the analytical method and its
detection limit was not specified. The hot spring and brine samples from the
surrounding of Dallol were not analyzed for lithium, which is the main motive for this
work. The presence of evaporite related mineral deposits in the Danakil depression
has been known before the World War II (Muzvondiwa et al., 2015). Warren, (2016)
has summarized the occurrence of potash in the Danakil depression and indicated the
Danakil brines as a source of CaCl2 (Fig. 4.4). The recent work by KIGAM and GSE,
(2012) and Tanarmu Industrial Chemical PLC, (2018) point out the need for further
study in the Danakil depression to know the potential occurrence of lithium in brines
and associated evaporite deposits.

34
Table 4. 2: The general exploration history of Lithium in Ethiopia and particularly in
Danakil depression (Source: Parsons Company, 1960; GSE and KIGAM, 2012;
Tanarmu Chemical PLC, 2018 (all are open file reports)).

Concession Work undertaken Results for the Company

period occurrence of lithium Name
1960 Conducted Survey in the Nil Parsons
Danakil depression mainly Company
aiming for potash, sulfur and
other minerals.

2012 Preliminary Survey of Rare Positive result (0.01 to KIGAM

Metal Mineralization in MER 6.2 ppm) and they gave and GSE
and part of Afar depression reccomendation the
aiming for epithermal Au and need for study on the
other minerals (K, Li, and S) uncovered part of
and other rare metal deposits Danakil and MER
out of the rift in Kenticha. lakes.

2018 Conducted detail sampling Positive result from Tanaramu

Mainly aiming for Bromine lake Afdera (0 to 9.8 Industrial
occurrence and additional for ppm) Chemical
Lithium in lake Afdera only. PLC

Figure 4. 4: World map showing Lithium and CaCl2 brine occurrences (Warren,
2016). The Red stars indicate operations that are on the stages of extracting lithium
brines in a saline setting. The green star indicates locations of possible future lithium
brine resources. The purple circle indicates an active CaCl2 brine operation; green
squares indicate other sites of CaCl2 that may be a future possible CaCl2 brine
resource. The brown circles and green shaded rectangular zones indicate the positions
of ancient marine halite and sulphate basins.

35
 CHAPTER FIVE

5.0 Geochemical Results

5.1 Geochemistry of Brines (Danakil and MER Lakes)

Out of 42 collected samples, 34 representative samples were analyzed for their
lithium content, major and trace element constituents. In addition the duplicate of 13
brine samples were analyzed again for their lithium content in EMPBC Laboratory to
confirm and compare the lithium values done by the ALS Geochemistry laboratory.
The lithium concentration of the hot springs and Danakil surface brines are relatively
higher than the MER lakes.

The geochemical results of the hot springs and brine lake waters (Table 5.1 and 5.2)
indicates, the northern part of the Afar depression, Dallol (sample number DH 1 and
DH 2) shows higher value 16 (20 ALS) ppm Li content compared with other samples
collected from the central and southern MER lake waters. Summary of the primary
geochemical result of Lithium and other related element is given in table 5.1 and 5.2.
Secondary geochemical data collected form KIGAM and GSE report and Tanarmu
Industrial P.L.C for different brine lakes and hot springs are presented in table 5.3 and
5.4 respectively.

The chemistry of the lake water from MER shows very low lithium brine
concentration ranges from <0.04 to 0.09 ppm. The surface brine and hot spring
samples from the surrounding of Dallol area indicates relatively high lithium content
ranges from 1 to 16.1 (20 ALS) ppm.

36
Table 5. 1: Geochemical Result of Brine samples (ALS Laboratory service, North
Vancouver, Canada). Samples values described as less than (<) or greater than sign
(>) are below and above the detection limit of the analytical instrument.

Samples
Field ID YD 1A YD 2A DL 1A DL 2A DL 3A DH 1 DH 2
Sample
Brine Hot spring
Type
Location Surface brine from the surrounding of Dallol Dallol
ICP-AES; IC (ppm)
Li <10 <10 <10 10 10 20 20
Cl 195000 196000 39100 102000 36200 210000 203000
F <5 <5 <2 5.1 <20 573 508
SO4 950 720 1510 883 490 9230 5240
Br 635 664 443 1350 465 359 318
NO3 (as N) <5 5 <5 <5 <5 <5 <5
NO2 (as N) <1 <1 <1 <1 <1 <1 <1
Ag <1 <1 <1 <1 <1 <1 <1
Al <100 <100 <100 <100 <100 400 600
As <10 <10 <10 <10 <10 <10 <10
B 19 6 12 38 10 498 663
Ba <10 <10 <10 <10 <10 <10 <10
Be <10 <0.1 <0.1 <0.1 <0.1 0.1 0.1
>1000
Ca 9220 >10000 0 >10000 9670 940 2800
Cd <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5
Co <2 <2 <2 <2 <2 <2 2
Cr <2 <2 <2 <2 <2 <2 <2
Cu <1 <1 <1 1 <1 19 3
Fe <100 <100 <100 <100 <100 >10000 >10000
K 3700 3000 1000 4300 1100 18000 14700
Mg 4180 5550 972 7380 1450 5200 4810
Mn 9 39 <1 74 <1 >1000 935
Mo <1 <1 <1 <1 <1 <1 <1
Na 111000 105500 14300 27300 11800 82900 81100
Ni <2 <2 <2 <2 <2 <2 2
P <100 <100 <100 <100 <100 100 100
Pb <5 <5 <5 <5 <5 <5 <5
Sb <5 <5 <5 5 <5 <5 <5
Sr 258 226 180 535 212 57 103
Ti <100 <100 <100 <100 <100 <100 <100
V <1 <1 <1 <1 <1 37 29
Zn <1 1 <1 <1 <1 84 76

37
Table 5.1: (Continued)

Samples CB CB CB CM AB WT
Field ID 01A 02A 03A 01A 01A 01A
Sample
Lake water River
Type
Chew Bahir Chamo Abaya Weyto
ICP-AES; IC (ppm)
Li <10 <10 <10 <10 <10 <10
Cl 19.3 78.8 37.4 147 59 3.4
F 0.75 1.12 0.9 7.22 7.35 0.22
SO4 16.9 <2 2.4 64.2 14.1 8.53
Br 0.15 0.47 <0.3 1.06 0.48 <0.05
NO3 (as N) <5 <5 <5 <5 <5 <5
NO2 (as N) <1 <1 <1 <1 <1 <1
Ag <1 <1 <1 <1 <1 <1
Al <100 <100 <100 <100 <100 <100
As <10 <10 <10 <10 <10 <10
B <5 <5 <5 <5 <5 <5
Ba <10 <10 <10 <10 <10 <10
Be <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
Ca <50 80 100 <50 <50 <50
Cd <0.5 <0.5 <0.5 <0.5 <0.5 <0.5
Co <2 <2 <2 <2 <2 <2
Cr <2 <2 <2 <2 <2 <2
Cu <1 <1 <1 <1 <1 <1
Fe <100 <100 <100 <100 <100 <100
K <500 <500 <500 <500 <500 <500
Mg 15 21 29 11 <5 5
Mn <1 1 3 <1 <1 <1
Mo <1 <1 <1 <1 <1 <1
Na 100 100 200 500 200 <100
Ni 2 <2 <2 <2 <2 <2
P <100 <100 <100 <100 <100 <100
Pb <5 <5 <5 <5 <5 <5
Sb <5 <5 <5 <5 <5 <5
Sr <2 <2 2 <2 <2 <2
Ti <100 <100 <100 <100 <100 <100
V <1 <1 <1 <1 <1 <1
Zn <1 4 <1 <1 <1 <1

38
The lithium versus strontium plot (Fig. 5.1A) indicates negative relation except
sample number DL-2A. The source of lithium can be from the erosion of felsic
igneous rocks, while strontium is from mafic sources. Since no isotope data are
available under this work, so that exact source determination of the brine was
uncertain. The scatter plot of Li vs potassium shows positive correlation (Fig. 5.1B).
The two hot spring samples placed on the plot differently from the other surface
brines, which clearly indicates the source of the hot spring is dissimilar with the other
brines.

Figure 5. 1: Scatter plot for brine samples (A) Li versus Sr (ppm), (B) Li Vs K (ppm).

39
Table 5. 2: Geochemical result of brines samples from Dallol, lake Abijata-Shala and
Lake Chew Bahir (EMPBC lab, Addis Ababa, Ethiopia). Those samples values
described as less than sign (<) and ND shows they are below the detection limit and
not detected by AAS.

Samples YD DL DH DH CB CB
Field ID YD 1A 2A DL 1A DL 2A 3A 1 2 01A 02A
Sample
Brine Hot spring Lake water
Type
Location Surface brine from the surrounding of Dallol Dallol Chew Bahir

AAS (ppm)
11149 1042 1180 8296 8145
+
Na 8 69 14301 28125 0 3 9 98.9 85.0
1989 1526
K+ 3849 3098 987 4698 1100 6 9 16.2 5.2
1298
Ca2+ 9756 7 9876 11259 9670 1203 2799 10.1 5.7
Mg2+ 4180 4987 894 8123 1450 5611 4910 11.3 2.6
<0.0
Li+ 1.9 2.1 4.2 9.8 8.5 17.2 16.1 4 <0.04
Fe+3 105.1 115.3 99.5 106 102 ND ND 0.7 0.7
120.
CO3-2 95.08 179.6 120 719.6 299.7 ND ND 1 32.1
SO4-2 950 720 2006 956 490 9006 5896 15.9 <2.0
20042 1989 3620 2101 1989
Cl- 5 72 39205 99569 0 56 63 18.3 81.2
PH 6.7 6.7 6.6 6.7 6.4 2.5 2.4 7.0 7.6
Table 5.2: (Continued)

Samples CB CM AB WT AB-
Field ID 03A 01A 01A 01A SH-1 AB-Pr Har AB-Cr
Sample Preconcentration to
Lake water River
Type Lake crystallization pond
Location Chew Chamo Abaya Weyto Shala
Abijata
Bahir
AAS (ppm)
Na + 102.0 251.0 39.0 50.3 11002 7985 26050 105296
+
K 10 5.6 2.3 2.3 238 382.45 714 2620
Ca2+ 5.3 4.6 3.2 5.2 0.33 0.10 0.09 0.09
Mg2+ 2.1 2.3 2.3 4.3 0.11 0.25 0.23 0.05
+
Li <0.04 <0.04 <0.04 <0.04 0.04 0.05 0.08 0.09
+3
Fe 1 0.5 <0.5 1.2 1.20 1.20 1.35 1.90
-2
CO3 71.9 78.3 11.2 23.6 4260 3695 19224 45240
-2
SO4 2.4 63.3 8.53 14.1 13935 9875 23054 118821
-
Cl 37.4 150 3.4 59 757.83 809.12 1025 12596
PH 7.4 7.6 7.5 7.6 9.10 9.20 9.50 10.10

40
The geochemical result of lithium from other sources for different lakes, springs, and
the detail sampling result of lithium concentration from Lake Afdera is given in table
5.3 and 5.4 respectively.

Table 5. 3: Geochemical data of Lithium and other related elements for the MER
lakes (Source: KIGAN and GSE, 2012) and the letter L stands to represent lake.

Lab Sample
Name K Na Ca Mg Li Sr
Results ID
KIGAM AB01 L- 476 11,240 2.45 0.32 0.1 0.1
GSE Abijata 19.3 12,155 2.6 20
KIGAM SH01 L-Shala 27 1,498 0.98 0.2 0.54 0.23
(Hot
GSE spring) 21.9 2,290 1 0.6
KIGAM SH02 L-Shala 198 5,750 5.29 0.85 0.14 0.1
GSE (Brine) 234 7,058 4.8 43
KIGAM LA01 L- 44.2 854 2.95 0.34 0.32 0.06
GSE Langano 38.5 741 2.9 0.3
KIGAM FA01 L- 19.5 390 2.3 2.31 0.01 0.06
Fentale
GSE (hot 18.1 373 1.9 1.8
spring)
KIGAM BE01 L- 45.7 2,174 3.19 0.57 0.040 0.06
Beseka
GSE 49.5 1,420 8.9 0.2
KIGAM AF01 L- 91.7 990 482 97.9 0.14 7.32
Afdera
GSE (hot 84 1560 3.9 81
spring)
KIGAM AF02 L- 2,494 38,628 14,138 1,028 6.2 197
GSE Afdera 281.8 42,760 14.2 980
(Brine)
KIGAM AS01 L-Asale 8,025 77,826 33,829 6,167 4.62 717
GSE 96.5 95,550 34,585 71.3
The concentration of lithium and potassium is elevated in the Danakil lakes (lake
Afdera and Asale) compared with the other hot springs and lakes of the MER (Table
5.3). The lithium values (Table 5.3) recorded from Lake Afdera and Asale, part of the
Danakil depression is 6.2 and 4.62 ppm respectively indicates relatively high values
compared with the other localities in the MER (KIGAM and GSE, 2012).
The lithium concentration from lake Afdera and the surrounding hot springs (Table
5.4) was recorded in the range of 0 to 9.8 ppm (Tanarmu Industrial Chemical P.L.C,

41
2018). The relative high lithium concentration values of lake Afdera recorded in
North-Eastern part of the lake (Fig. 5.2 and Fig. 5.3).

Table 5. 4: Geochemical Results of brine and hot spring samples for their lithium
constituents (Tanarmu Industrial Chemical P.L.C., 2018).

Sample Coordinates Li+ Sample Coordinates Samp Li+

Sampl
le
X Y e Type ppm X Y ppm
Type
1465113.54 703341.56 Brine 5.44 1470295.74 709783.92 Brine 5.18
1464030.34 705392.11 Brine 5.42 1470878.50 708691.84 Brine 4.92
1464030.34 705392.11 Brine 5.12 1470878.50 708691.84 Brine 9.8
1463083.54 707260.12 Brine 5.18 1471527.26 707454.58 Brine 8.82
1463083.54 707260.12 Brine 5.24 1472577.68 708685.42 Brine 5.56
1462620.15 708314.39 Brine 5.14 1471952.89 709879.64 Brine 4.9
1461090.43 707966.47 Brine 5.02 1473881.26 710858.53 Brine 5.54
1461762.95 706548.00 Brine 5.32 1473881.26 710858.53 Brine 5.56
1462701.56 704766.12 Brine 5.08 1473658.93 709871.11 Brine 5.08
1462701.56 704766.12 Brine 4.96 1473658.93 709871.11 Brine 1
1463352.81 703675.47 Brine 5.42 1476260.06 711361.84 Brine 4.74
1461403.64 704084.16 Brine 4.96 1476260.06 711361.84 Brine 4.72
1460457.70 705844.05 Brine 4.66 1475159.82 713403.93 Brine 4.98
1459946.25 706907.40 Brine 5.02 1476511.98 714083.44 Brine 5.7
1459152.20 705186.45 Brine 5.84 1476511.98 714083.44 Brine 5.12
1459918.99 703775.05 Brine 5.1 1476511.98 714083.44 Brine 5.02
1467159.93 702885.93 Brine 5.06 1477346.50 712889.59 Brine 5.5
1466460.35 704191.25 Brine 5.08 1477346.50 712889.59 Brine 5
1466460.35 704191.25 Brine 5.26 1477346.50 712889.59 Brine 4.6
1465658.10 705808.28 Brine 5 1477346.50 712889.59 Brine 5.66
1465658.10 705808.28 Brine 4.62 1477346.50 712889.59 Brine 8.74
1465658.10 705808.28 Brine 5.02 1477346.50 712889.59 Brine 5.38
1465658.10 705808.28 Brine 5.22 1477935.38 711347.14 Brine 5.42
1464490.29 707920.63 Brine 4.88 1477935.38 711347.14 Brine 5.72
1464490.29 707920.63 Brine 5.04 1479642.01 711370.42 Brine 5.54
1463852.34 709138.06 Brine 5.36 1479642.01 711370.42 Brine 4.98
1465817.06 708654.37 Brine 4.9 1479642.01 711370.42 Brine 5.74
1466654.19 707240.63 Brine 4.98 1479000.73 712591.17 Brine 5.62
1466654.19 707240.63 Brine 4.88 1479000.73 712591.17 Brine 5.28

42
Table 5.4: Continued

Sample Coordinates Sample Li+ Sample Coordinates Sampl Li+

X Y Type ppm X Y e Type ppm
1467210.16 705971.61 Brine 5.1 1479000.73 712591.17 Brine 4.78
1467210.16 705971.61 Brine 4.9 1479000.73 712591.17 Brine 5.12
1467210.16 705971.61 Brine 4.54 1479000.73 712591.17 Brine 4.4
1467210.16 705971.61 Brine 4.8 1479000.73 712591.17 Brine 4.66
1467210.16 705971.61 Brine 4.7 1478152.48 714151.66 Brine 4.78
1468601.27 703367.39 Brine 5.58 1478152.48 714151.66 Brine 5.04
1468601.27 703367.39 Brine 3.5 1478152.48 714151.66 Brine 5.1
1469319.21 702059.70 Brine 5.34 1480304.49 713316.21 Brine 4.64
1470426.63 703086.44 Brine 4.34 1480304.49 713316.21 Brine 5.16
1469321.03 705225.09 Brine 5.3 1480304.49 713316.21 Brine 4.48
1469321.03 705225.09 Brine 5.76 1480942.21 712213.00 Brine 4.86
1469321.03 705225.09 Brine 5.04 1480942.21 712213.00 Brine 5.52
1468350.30 707030.81 Brine 5 1480942.21 712213.00 Brine 5.7
1468350.30 707030.81 Brine 4.58 1467742.29 705748.76 Brine 5.2
1467698.86 708324.32 Brine 5.34 1462409.52 702975.48 Spring 0.08
1471329.92 704608.79 Brine 4.84 1462589.52 703075.71 Spring 0.13
1471918.38 706367.27 Brine 4.64 1460824.16 702852.11 Spring 0.16
1470288.84 706503.52 Brine 5.2 1463846.91 710501.16 Spring 0.39
1470288.84 706503.52 Brine 5.6 1463997.59 710160.83 Spring 0.42
1470288.84 706503.52 Brine 4.8 1466308.97 710253.29 Spring 0.49
1469358.23 708258.71 Brine 4.88 1464786.97 702048.73 Spring 0
0.00
1469358.23 708258.71 Brine 5.1 1458537.50 702876.37 Spring
08

43
KIGAM and GSE (2012), open file report, shows the lithium concentration from the
surrounding of lake Afdera hot spring is 0.14 ppm and the brine lake water have
lithium content 6.2 ppm, and this is the highest lithium value during their
investigation and they recommend the brines of the Danakil depression needs further
investigation for their lithium content. The geochemical results of 92 brine samples
(Fig. 5.2 and 5.3) from lake Afdera shows the lithium concentration ranges from 1 to
9.8 ppm with average values 5.3 ppm of lithium. In addition, 7 hot spring samples
from the surrounding of lake Afdera displays lithium concentration ranges from
0.0008 to 0.49 ppm with average concentration 0.24 ppm (Tanarmu Industrial
Chemical P.L.C., 2018, open file report).

Figure 5. 2: The general outline of lake Afdera and contour map of the lake from its
lithium values, the red cross indicates the location of the sample points with
respective lithium values. The lithium concentration from the lake shows
inhomogeous distribution. The elevated lithium concentration was recorded in North-
Eastern part of the lake, which can be feed by hot springs passing through felsic
volcanic rocks that give rise to relatively high lithium content on that spot.

44
Figure 5. 3: Digital elevation map of lake Afdera from its lithium values, the red
cross indicates the location of each sample points with respective lithium values.

5.2 Geochemistry of Rocks

The geochemical result from the Danakil evaporite deposit (Table 5.5) shows low
lithium concentration and it is in the range of the average concentration of lithium in
most rocks. The evaporite bearing horizon (upper and lower carnallitite) shows
elevated lithium concentration (20 ppm) and one the bischoftite unit has 40 ppm, but
it is not a potash bearing horizon.

45
Table 5. 5: Geochemical result of the rock samples from Dallol area, Danakil
depression. The sign (<) and (>) indicates the ICP-AES limit of detection below and
above respectively for that particular elements and oxides.

Samples B1Y- B1Y- B1Y-

Field ID CR-7 CR-3 CR-9 HA-3 UHA YSY UCAR YBS LCAR

from last test

Upper halite
Halite from

Bischofite
(Carnalite
Lithology

Rock salt
type salt)

carnalite

carnalite
salt flat
Kainite

Sylvite
CTMS

Lower
Upper
pond

unit
ICP-AES (%)
SO4 19.6 1.14 1.38 0.39 0.33 4.58 >30.0 2.07 22.6
SiO2 1.24 0.07 0.85 0.36 0.08 0.07 0.1 0.05 0.1
Al2O3 0.27 0.01 0.13 0.09 0.01 <0.01 0.02 <0.01 0.02
Fe2O3 0.22 0.01 0.13 0.08 0.02 0.02 0.03 0.02 0.02
CaO 0.5 0.54 0.81 0.66 0.24 2.53 4.51 0.02 0.35
MgO 8 0.62 0.08 0.23 0.05 0.34 15.9 20.2 17.15
Na2O 20.9 28.6 41.8 48.5 49.4 46.2 12.25 0.57 7.03
K2O 13.35 22.1 7.15 0.4 0.19 0.25 3.92 0.34 7.96
Cr2O3 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002
TiO2 0.04 <0.01 0.02 0.01 0.01 <0.01 <0.01 <0.01 <0.01
MnO 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
P2O5 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
SrO <0.01 <0.01 0.01 0.01 <0.01 0.02 0.04 <0.01 0.01
BaO <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
ICP-AES; IC (ppm)
Li <10 <10 <10 <10 <10 <10 20 <10 20
Cl >20000 >20000 >20000 >20000 >20000 >20000 >20000 >20000 >20000
F 70 <20 <20 <20 <20 <20 160 <20 120
Rb 90 20 10 <10 <10 10 30 <10 60

46
Table 5.5: (Continued)

Samples B1Y- B1Y- B2C- B2C- B2C- B2C-

Field ID KA LHA SY UCAR B2C-B LCAR B2C-K LHA

Bischofit
Litholog

carnalite

carnalite
Kainite

Kainite
Sylvite
Lower

Lower

Lower
Upper
halite

halite
y

e
ICP-AES (%)
SO4 13.35 1.89 1.32 2.4 >30.0 25.3 >30.0 2.67
SiO2 0.11 0.06 0.13 0.3 0.17 0.27 0.03 0.22
Al2O3 <0.01 0.01 0.02 0.08 0.03 0.04 <0.01 0.04
Fe2O3 0.01 0.05 0.05 0.08 0.04 0.05 0.01 0.06
CaO 0.17 0.43 0.72 1.31 0.42 0.12 0.17 0.83
MgO 5.46 0.57 0.08 0.15 19.05 18.25 15.7 0.65
Na2O 33.9 48.4 49.2 34.6 10.05 4.84 4.22 46.8
K2O 5.47 0.65 0.3 14.85 4.67 8.2 16.4 0.62
Cr2O3 0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002 <0.002
TiO2 <0.01 0.01 0.01 0.01 0.01 <0.01 <0.01 <0.01
MnO <0.01 <0.01 0.01 0.01 0.01 <0.01 <0.01 <0.01
P2O5 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
SrO <0.01 <0.01 0.01 0.02 0.01 <0.01 <0.01 0.02
BaO <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
ICP-AES; IC (ppm)
Li <10 <10 <10 <10 40 20 <10 <10
Cl >20000 >20000 >20000 >20000 >20000 >20000 >20000 >20000
F <20 <20 <20 <20 620 90 <20 <20
Rb 10 10 10 30 120 80 30 <10

47
Figure 5. 4: Scatter plots for rock samples Li Vs Rb and Li Vs F.
The scatter plot (Fig. 5.4) of Li against rubidium and fluorine indicates positive
correlation except the deviation of one sample (B1Y-UCAR). Due to the limited
analytical result, exact source determination for lithium was undefined. The positive
correlation of lithium versus rubidium can suggest, the lithium element is possibly
derived from felsic igneous or the surrounding basement and sedimentary rocks. In
addition, lithium can be accumulated during the formation of the K and Mg-rich
potash bearing evaporite sequences. The enrichment of lithium has positively
correlated with rubidium and potassium; this indicates the lithium is formed during
the precipitation of K-Mg salts, which is the Carnallitite Units (Fig. 5.5). The positive
correlation between lithium Vs fluorine can also give other possible hint that the
lithium can be derived from felsic igneous rocks. The lithium concentration shows
negative correlation with potassium (Fig. 5.6) in Bischoftite Units which is Mg-rich

48
horizon; this indicates the lithium is precipitated during the precipitation of the Mg
salts. The lithium stay in solution until the precipitation of K-Mg salts (carnallite and
bischofite) which are the last stage of the precipitation serious in the ideal sea water
evaporation as Babel & Schreiber, (2014). The plot of lithium with other elements
(Fig. 5.5 and 5.6) denote point samples of the drill cores and composite sampling was
not possible in the field due to the availability of limited quartered drill cores.

49
Figure 5. 5: Bore Hole 2 Stratigraphic section Vs linear graph of Li, Rb, F, K2O,
MgO, CaO, Na2O, and SrO. The lithium is enriched in the lower and upper carnallitite
unit, which is the potash bearing horizon.

50
Figure 5. 6: Bore Hole 1 Stratigraphic section Vs linear graph of Li, Rb, F, K2O,
MgO, CaO, Na2O, and SrO.
It shows the same type of trend like the bar graphs. The linear graph of this section
indicates the lithium is enriched in the carnallite and bischofite horizons. The lithium
plot also shows the same trend with rubidium, fluorine and magnesium.

51
 CHAPTER SIX

6.0 Comments on Economic Extraction of Lithium during

Potash Mining in Danakil Depression

6.1 Present Status of Lithium-Brine Extraction Technologies

Lithium brine deposits in the world are widely distributed, but only limited of them
are concentrated adequate to potentially capable for exploitation. The work by Kesler
et al., (2012), Vikstrom et al., (2013) and Kunasz, (2006), shows the current
commercial extractable lithium were comes from a little high grade lithium brines
deposits.
Exploitation of lithium brines starts with brine being pumped from the ground into
evaporation ponds. The actual evaporation is enabled by incoming solar radiation, and
the operation should be located in sunny areas with low annual precipitation rate. The
net evaporation rate determines the area of the required ponds. It can easily take
between one and two years before the final product is ready to be used, but certain
places submitted to the effects or winter or high precipitation can take even longer.
Due to the long periods required for production of lithium from brine deposit by solar
evaporation, it can make brine deposits hard adequate for sudden changes in demand
(Evans, 2008).

Lithium salts are extracted from water in mineral springs, brine pools, and brine
deposits, and mining lithium metal is not expensive, where lithium is collected from
brine ponds evaporated by the sun. Lithium brine extraction technology widely used
in today’s actual mining of lithium ores (Kaskey, 2014). Lithium is present in
seawater, but commercially viable methods of extraction have yet to be developed
(Martin, 2015).

The extraction technologies of lithium (Fig. 6.1), in addition to the common solar
evaporation techniques, from brine deposits at different scale of production include
calcination, adsorption, extraction and membrane separation (He et al., 2017).
The technology of Calcination to produce lithium involves, the pumped and
distributed brine is dry to get a solid mixture of MgCl2.2H2O and LiCl. After
Carbonation to MgO and LiCl at a temperature of 800 to 1000 0C, the LiCl is
dissolved because of the solubility of MgO is low; LiCl is then precipitated to

52
Li2CO3. This technology is mature but it has high energy cost and pollute the air due
to the emission of acid haze.

Adsorption is the other technology to extract lithium and it involves the Li-ion sieve.
This method involves the absorption of lithium ion by lithium ion selective sieve from
brine, then by dilute HCl solution to obtain a lithium-rich solution. It has low cost and
easy to realize larger scale. Dissolution of adsorbent reduced adsorbing capacity due
to blockage of the ion channels.

Extraction includes the organic extractants that can capable of selectively extract Li
from brine. Though for this method, suitable extracting equipment with small outline,
low cost, high efficiency is required.

Membrane involves electro-dialysis in which monovalent and divalent cations

diffuse at different speeds in electric field across the ion exchange membrane;
separation occurs for Li and Mg ion. Nanofiltration membrane separates monovalent
ions and divalent ions; thus is able to separate Mg; the brine has to be diluted to
reduce osmotic pressure. Easy to control and low energy consumption, but it is
emerging technology and no commercial membrane system available today.

Figure 6. 1: Overview of Emerging Brine Technologies (Saxton, 2018).

53
 6.2 Possibility of Lithium Extraction in the Danakil Potash
Project
The finding of this research come up with the lithium concentration from the MER
lakes (<0.004 to 0.09 ppm) were in the average range of natural water concentration.
The previous work by KIGAM and GES (2012) presented the lithium content from
MER lakes and hot springs was ranges from 0.01 to 0.54 ppm. The lithium
concentration from the Danakil depression displays relatively enriched compared with
the MER lakes and hot springs. The lake brines and hot springs from the Danakil
depression has a lithium content range from 1.9 to 16.1 (20 ALS) ppm. The lithium
was elevated in the Dallol hot spring compared with the brines of the country and its
concentration is 16.1 (20) ppm.

The concentration of lithium from the evaporite rock samples ranges from 20 to 40
ppm. This value is very low in rocks and it is in the range of the back ground values
as described by Evans, (2014) and Kunasz, (2006).

During the planned solution mining approach for potash, large volume of potassium
bearing evaporites are dissolved underground and the brine treated on the surface in
multistage evaporation ponds (Muzvondiwa et al., 2015). It can be expected that the
total lithium content of the evaporites go in to solution during leaching and can be
extracted during the evaporation process for potash separation on surface.
Considering the large mining rate and total tonnage of the potash deposit of the upper
and lower carnallitite unit in the Circum potash license area an estimation of inferred
lithium resource was attempted as follows:-

Assumed average lithium content...................20 ppm (in Upper and Lower Carnallitite
units see chapter 5, Table 5.1, 5.2.)

Total tonnage of the potash.................~350 x 109 ton (Upper + Lower Carnallitite:

source Muzvondiwa et al., 2015)

Lithium resource in evaporite units ……………………….~7, 000,000 ton.

Mining Rate................................................2,000,000 ton/year of potash

Then, if only a fraction of 50% of the lithium is extractable we would still look at
~3,000,000 ton of lithium from the potash bearing evaporite units.

54
The price of lithium in 2017 was $9,100 per ton and the price increased dramatically
and reached $16, 000 in 2018 (Lithium, 2018 (https://www. metalary. com/lithium-
price/2018)).

As Jaskula, (2019) describes the annual average U.S. lithium carbonate price was
$17,300 per metric ton in 2018, which increases a 15% of price from 2017 (Jaskula,
2019). Based on the values of lithium $17,300/metric ton (Jaskula, 2018), the lithium
concentration in Danakil evaporite horizon can reach level of economic as a
byproduct for the potash company. However, the price of lithium carbonate in China
decreased from ~$21,000 per ton at the beginning of the year 2019 to ~$12,000 per
ton in the third quarter due to the high production of lithium than the world
consumption (Jaskula, 2019).

55
 CHAPTER SEVEN

7. Discussion

7.1 Brines (Danakil Depression)

The present study checked the hypothesis whether the enrichment of Li in brines
according to the USGS model conditions is applicable in the Danakil depression. The
findings of this research indicate that the lithium content is enriched in the northern
end of Danakil depression and very low in the Main Ethiopian Rift lakes. However,
the concentration of lithium in the Danakil depression is still below the current cutoff
grade value of brines 200 ppm (Bradley et al., 2013) for economic extraction of
lithium. If the global demand for lithium is increasing considerably in the future as
predicted by most economists, the lithium occurrence in the evaporite unit of the
Danakil may well reach the level for economic extraction as a byproduct for the
potash company. Further detailed exploration is needed to outline the locations and
source of the highest lithium concentrations in the Danakil brines.

Technological development towards lower cost lithium extraction methods will also
bring the Danakil brines in to focus for economic extraction as a byproduct of
exploitation of other commodities like bromine from brines or potash from evaporite
source rocks. Extraction of lithium form the Danakil potash horizon does not need
additional techniques, and it wants only taking the end brine solution of the potash
and evaporates it in different evaporation ponds.

The average concentration of lithium in different water bodies are given under
Nicolas (2017) and the concentration of lithium in ground water bodies are well
described by Vilma et al., (2017). The lithium concentration in brines of Ethiopia can
be comparable with the lithium brine content (~0.035 ppm) described by Nicolas,
(2017) and Vilma et al., (2017).

Geological processes like marine flooding and volcanic activity in the Danakil
depression have created lithium concentration to be elevated in the Dallol hot springs
and the surrounding surface brines. The source of the lithium is ultimately unknown,
but it can be a meteoric water source or juvenile water which involves alteration of
silicates (particularly Li- and K-bearing minerals) by the action of hot water or influx

56
through surface water run-off from the escarpments. The Danakil Depression
characterized by extreme hydrothermal activity with potash occurrences and it is
related to the rift magmatism, marine flooding, and deep brine cycling (Warren,
2016). Since, currently no isotope data available for the brine samples, so the source
of the brine is uncertain.

Brines samples from the Danakil depression can be separated geochemically in to two
types as hot spring and surface brines. The multi-element diagrams (Fig. 7.1a and
7.1b) show a marked difference between hot spring brine and surface brines in the
Danakil.
The hot spring brines (Fig. 7.1a and 7.1c represented by dash lines) are enhanced in
Li, K, Na, Mg and depleted in Ca and Sr. Surface brines (Fig. 7.1a and 7.1c,
represented by solid lines) show a lower level of lithium and Mg combined with
strongly elevated Na-, Ca- and Sr-values. An exception is the sample DL-2A (pond
sample close to Circum fly camp) which shows the highest lithium value for the
surface brines combined with low Na and high Ca, Mg, and Sr.

The relative low values of Ca give a hint to the source of the brine is closer to ocean
or sea water. While, the surface brines samples from the surrounding of Dallol directs
the opposite trend with the plot of the hot spring. The high values of Ca in surface
brines can suggest the source of the brine would be non-sea water or meteoric water.
In addition the opposite trend between the hot springs and surface brines of the
Danakil indicate the source of the brine that hosts the lithium is different and the
interaction of the brine from the surrounding geologic material and the environment
makes the availability of the elements to be dissimilar.

57
Figure 7. 1: Log scale multi-element plot of (a) Dallol hot spring; (b) Surface brines
in the surrounding of Dallol, and (c) Combined plot of both surface brines and hot
springs. The description of the samples plotted as YD-1A, YD-2A, DL-1A, DL-2A,
DL-3A, DH-1and DH-2 are given in chapter five table 5.1 and 5.2.
The lithium and potassium in the Danakil depression apparently originated from
currently flowing hot springs, with the current brine composition being a blend of
evaporated water from these springs and surface and ground water that drains into the
basin. During several periods of evaporation halite was crystallized, forming
occasional beds in the alluvial sediments.

58
Figure 7. 2: Scatter plot of Li Vs F, K and Sr for Dallol samples.
The scatter diagram (Fig. 7.2) shows lithium is positively correlated with K and F;
and it indicates negative correlation with Sr and Ca. The positive correlation of
lithium with K can give a hint that the lithium is derived from K-rich evaporite units
like Carnallitite. The Dallol hot spring displays perfectly different appearance with
respect to the surrounding surface brines and their trend is clearly visible (Fig. 7.1c)
by their Ca and Sr plots. The negative correlation between lithium and Ca can be
interpreted as the Ca is precipitated in the early stage of evaporation and the lithium
stay in solution until the start of K-Mg salts precipitation and this is in accordance
with Babel & Schreiber, (2014). Strontium and calcium have similar chemistry and
their occurrence in different type of rock shows similar trends (Skougstad and Horr,
1963). He also noted that, the source of Sr in natural water is igneous, metamorphic
rocks and trace amount from limestone, and it shows similar proportion with Ca when
it derived from these rocks. The Ca and Sr values in the hot spring is lower and shows

59
inverse relation with the surface brines which indicates the hot water that give rise to
the highest lithium concentration in the area is sourced from sea water. The Ca and Sr
plots in the surface brines shows enhancement compared with the Dallol hot springs.

The negative trend of Sr and Ca in the hot spring and surface brines of the Danakil
depression has implications for a hint on the source of geologic material (either K-Mg
rich evaporites or felsic igneous rocks) that give rise to the occurrence of lithium brine
in the area. But consideration of additional factors which can affect the behavior of
strontium when it is dissolved in water should be considered because the movement
of the water through the rock can change the chemistry and constituent of Sr in the
water. Generally, the highest the lithium content the hot spring has lower in Sr and
Ca values, whereas the low lithium content from the surface brines displays high Sr
and Ca values compared with the hot springs.

7.2 Brines (MER Lakes)

The present work on the MER lakes revealed the lithium concentration is very low
and it is in the back ground values of lithium concentration in fresh water. Lake Shala
which is fed by hydrothermal spring shows slightly elevated in lithium (0.04 mg/L).
But pervious work by KIGAM and GSE (2012) also indicates even more the lithium
is enriched than the current result. The hot spring that fed lake Shala has 0.54 mg/L of
Li and the lake itself gets more diluted with lithium content 0.14 mg/L (KIGAM and
GSE, 2012) and the other rift lakes and hot springs (e.g. Langano, Beseka, Dofan,
Fentale) show background values of sea and natural fresh water lithium contents. A
review data by Kavanagh et al. (2017) noted the lithium content in drinking waters
ranges in concentration from 0.0007mg/L in Japan to 0.19 mg/L in Portugal and other
countries including Texas and England are in the range between the above
concentration. Considering the background values of lithium in natural water, no Li
indication in the MER lakes and unusual hot spring and geothermal brines from the
rift are not sampled. The multi-element plot (Fig. 7.3) shows for Abijata-Shala
depletion of Ca and Mg and enrichment of K and Na compared with the other lake
Chew Bahir, Abaya and Chamo. Lithium brine in the Abijata-Shala Soda ash
processing plant display the increment of Li from 0.04 to 0.09 ppm which is at least
two fold of lithium concentration in the last stage of the crystallization pond. Lithium
versus potassium indicates positive correlation in the soda-ash processing and parallel

60
goes to the enhancement of lithium. This will be an important hint during the potash
processing technology in the Danakil depression.

Figure 7. 3: Log scale multi-element diagram of the Main Ethiopian Rift lake
samples. The description of the samples CB-01A, CB-02A, CB-03A, CM-01A, WT-
01A, AB-01A, AB-01, AB-02, AB-03 and AB-04 are given in chapter five table 5.1
and 5.2.

7.3 Comparison of some selected world known lithium brine

deposit with the occurrence in Ethiopia
Except the Main Ethiopian Rift lakes, brines from the Danakil depression has lithium
indication. The lithium occurrence in the surface brine of the Danakil depression
ranges from 1.9 to 9.8 ppm, which is at least two fold less than the Dead sea lithium
brine deposits 12 (18) ppm as (Tandy and Canfy 1993; Epstein et al., 1981). But, the
lithium content in the Dallol hot spring ranges 16.2 (20) ppm which is equivalent to
the Dead Sea lithium brine deposit.

The Dead Sea lithium concentration in the sea water reaches 18 ppm and this lithium
content rises to 40 ppm in the end brines during evaporation and crystallization of
salts during potash production (Epstein et al., 1981). Other scholar, Tandy and Canfy
(1993), describes the lithium content of the Dead Sea brine is 12 ppm and raised in
the end brine to 23 ppm (sometimes 30 ppm). The increase in lithium concentration
during the potash production from Dead Sea and the raise of lithium concentration in
Abijata-Shala Soda Ash production (0.004 to 0.009 ppm) is more than two fold from
the original lithium concentration; which is an important hint for the proposed potash
extraction in the Danakil depression.

61
Brines from the Danakil depression has lithium concentration from the ground water
system 1.9 ppm, surface brines and ponds 2.1 to 9.8 ppm and the hot spring ranges
from 16 to 20 ppm and those values can be comparable with some Dead sea and
Clayton valley brine samples. The Lithium content in Clayton Valley from diverse
water bodies reported as the cold springs contains <1 ppm, one hot spring contains 1.6
ppm, the fresh ground water well is <1 ppm, and the hot groundwater located
northeast of Silver Peak in Clayton Valley contains 40.8 ppm of lithium (Munk, L.,
2011). But, the current extractable lithium brine deposit in the valley has lithium
concentration ranges from 200 to 5000 ppm (Barret and O’Neill, 1970; Brown and
Beckerman, 1990). Lithium concentration in sea water is examined to be 0.18 to 0.20
ppm and even this value is low, it is additional source of lithium in the world
(Takeuchi, 1980).

The lithium content from the surface brines and the Dallol hot springs are 10 to 45
and 80 to 85 times higher than the sea water lithium concentration.

Understanding the conditions for the formation of lithium brine and geological setting
of the known lithium brine deposit is important to compare the occurrence of lithium
brine in Ethiopia. The northern Chile, the place where the highest lithium brine
concentration found, was characterized by closed basins with active tectonic activity,
and the geology of the surrounding area is given in Hiner, J. E. (2017). The average
lithium concentration in the northern Chile (Table 7.1 and Fig. 7.4) testified as 0.1,
8.3 and 1500 (~7000) ppm in river, hot spring and Salar de Atacama respectively
(CORFO, 1981; Garrett, 1998).

62
Table 7. 1: Summary of lithium concentration in the known lithium brine deposits of
the world (Source of data: Garrett, 1998; CORFO, 1981; Barret and O’Neill, 1970;
Anon, 1966; Brown and Beckerman, 1990; Tandy and Canfy, 1993; Mohr et al.,
2010).

Concentration (ppm)
Reference
Location Li K Na Mg Ca
Hot Springs,
Chile 8.3 200 1210 28 135
Rivers, Chile 0.1 2.8 23 4.3 1
Surire, Chile 340 8700 54000 1250 750
349 7200 87200 6500 463
Garrett (1998)
Salar de Uyuni, 625 11700 70600 12500 306
Bolivia 321 6600 82000 6400 456
349 7200 87200 6500 463
Playa, Bolivia 69 514.3 4480 67 212
Salar de 1570 23600 91000 9650 450
Atacama, Chile 1500 18400 80000 9300 300 CORFO (1981)
400 8000 62000 400 500 Barret and O’Neill
5000 48000 78000 70 40 (1970)
Clayton Valley
400 10000 75000 600 500 Anon. (1966)
Brine, Nevada
Brown and Beckerman
200 800 6200 200 200 (1990)
1290
Dead Sea (Brine) 12 5600 30100 30900 0 Tandy and Canfy
Dead Sea (End- 2650 (1993)
Liquor) 23 2200 3800 70100 0
Great Salt Low,
USA 18 2600 37000 5000 160
Great Salt High,
USA 40 7200 87000 10000 360
Mohr et al., (2010)
Smackover Low, 2910
USA 146 2400 54900 2900 0
Smackover High, 3450
USA 386 5900 67000 3400 0

The enhancement of lithium concentration (Fig. 7.4) from hot spring, river and brines
of Salar de Atacama ( northern Chile), Salar de Uyuni (Bolivia), Great Salt lake and
Smackover (USA), Clayton valley (Nevada) and Dead Sea (Israel) shows positive
correlation with the enrichment of potassium. The lithium brine occurrence in Dallol
(Fig. 7.5) also shows the same trend with the current known lithium brine deposits.

63
Figure 7. 4: Log scale multi-element plot of lithium and associated elements from the
world known lithium brine deposits Garrett (1998); CORFO (1981); Barret and
O’Neill (1970); Anon. (1966); Brown and Beckerman (1990); Tandy and Canfy
(1993). The log scale concentration is ppm.

Figure 7. 5: Combined log scale multi-element plot of Dallol surface brines and hot
springs. The dash line represents Dallol hot springs and the solid lines represent the
surface brines of the Dallol area.

64
The lithium occurrence in the Danakil depression shows at least more than 90 fold of
the average sea and ocean water Li concentration (Table 7.2). But in the current
technology this amount of lithium concentration 16.1 (20) ppm is not economical and
it is 10 to 20 times less than the current exploitable lithium brine deposits cutoff grade
value (200 ppm) as described in Bradley et al., (2013). Lithium extraction form
Danakil brines and evaporite alone is not possible but can use as byproduct for the
potash company. The concentration of lithium (20 ppm) in potash bearing evaporites
of the Danakil can be comparable with the lithium concentration in Dead Sea (12
ppm) which is extracted as by product of the potash as Tandy and Canfy (1993).

Table 7. 2: Lithium concentration in different water bodies of the world and

Comparison with the current research work.

Range of lithium concentration in different water

Source
bodies (ppm)
Dallol Hot spring 16.2-20 This work
Dallol surface brines 1.9-9.8 This work
Main Ethiopian Rift This work
<0.04-0.09 (0.54)
lakes KIGAM and GSE, (2012)
Riley and Tongudai (1964)
0.17-0.2
Ocean and Sea water Angino and Billings (1966)
Public Drinking Water 0.000048-0.03553 Vilma et al., (2017)
Fresh water 0.001- 0.003 https://www.water-
Brines 0.05-2000 (7000) research.net/index.php/lithium
Vikström et al., 2013;
<0.2-0.24 (0.17) https://www.water-
Ground Water research.net/index.php/lithiu
Bradley et al. (2013);
200-1400
Current cut-off grade Bradley and McCauley
(160- 1400)
(2016)
Dead Sea (Brine) 12
Tandy and Canfy (1993)
Barret and O’Neill (1970)
Clayton Valley Brine, Anon. (1966)
200-400
Nevada Brown and Beckerman
(1990)
Salar de Atacama, Garrett (1998)
1500-1570
Chile CORFO (1981)

65
Figure 7. 6: Bar graph showing the comparisons of lithium contents from different
water bodies with the current research lithium brine content (Figure not to scale). The
lithium values are adjusted by correction factors to allow easy display in the graph.
The vertical dash line is used to split the lithium concentration of different water
bodies in ppb and ppm.

7.4 Rock samples from Danakil depression

The evaporite rock samples from the Danakil depression reveal a lithium
concentration in the range of common background values of the lithium content in
most rocks. Out of 17 rock samples, 13 of them are below detection limit (<10 ppm)
and 3 of the Carnallitite units shows 20 ppm and 1 samples from the Bischoftite unit
have a lithium concentration 40 ppm. The lithium concentration in the bischoftite unit
was not considered as a byproduct, because it is not a potash bearing horizon.
The concentration of lithium in the potassium and magnesium chloride horizons can
be explained by simple sea water evaporation in a closed basin. During this
evaporation process lithium is being enriched in the remaining brine at least until the
start of potassium and magnesium chlorides (Carnallite, bischofite) (see Babel and
Schreiber, 2014). The binary plot of lithium versus rubidium (Fig. 7.7) shows positive
correlation, and this enrichment of lithium in the potassium and magnesium salts
(Carnallite and Bischofite) can support the idea of sea water evaporation. During the
start of halite precipitation at lower evaporation levels of 10-20% evaporation lithium

66
stay in solution and it accumulated until the potassium and magnesium salt
precipitation.

In summary, lithium in the Danakil evaporites is strongly associated with the potash
bearing horizons not with the halite sequence.

Figure 7. 7: Scatter plot of Li Vs Rb.

7.5 Petrographic observations

Thin sections were prepared on a limited number of core samples from the K-rich
evaporite sequence. Petrographic features are used to interpret the evaporite units in
terms of primary sedimentary origin or secondary modification by leaching and
precipitation. In addition the variation of lithium values can be correlated with
petrographic observations. Elevated lithium concentrations were found in the Lower
and Upper Carnallitite and the Bischofitite Units. All three units show primary

67
sedimentary bedding with a variation in fine to medium grained salts associated with
minor clay fraction.

The lower Halite Unit is characterized by coarse euhedral halite crystals with distinct
oscillatory zoning (Fig. 7.8: P1f and P2f) and trails of fluid inclusions marking the
crystal surface during the various stages of the halite growth. This type of halite
growth is similar to bottom growth under shallow brine cover (Schreibber and El
Tabakh, 2000).

In contrasts the sylvitite layer (Fig. 7.8: P1a and P2a) shows coarse grained sylvite,
anhedral with irregular shaped fluid inclusions, mostly randomly distributed in the
crystals. Those petrographic observations support the interpretation of the sylvite as a
secondary mineral. Holwerda and Hutchison (1968) assumed that part of the sylvitite
unit was formed by selective leaching of MgCl2 from an original carnallite-rich layer.
The upper carnallitite unit (Fig. 7.8: P1b and P2b) showing primary sedimentary
layering with alternation of halite and carnallite crystals. The bischoftite horizon ( Fig.
7.8: P1c and P2c) is dominated by halite crystals with finely distributed bischofite.
The lower carnallitite unit (Fig. 7.8: P1d and P2d) is characterized by typical layering
of fine and coarse grain carnallite and halite crystals which is a feature of sedimentary
banding. The kainitite horizon (Fig. 7.8: P1e and P2e) considered as primary origin by
its large cubic crystals of halite and small carnallite crystals that form primary
layering.

68
 HA

Figure 7. 8: Generalized Stratigraphic section of the evaporite sequence with the

position of the thin sections micrograph. Thin section micrograph of (P1a & P2a)
sylvinite, (P1b & P2b) upper carnallitite, (P1c & P2c) bischoftite, (P1d & P2d) lower
carnallitite, (P1e & P2e) kainitite and (P1f & P2f) lower halite units. The description
of each thin section micrograph is given in table 7.3.

69
Table 7. 3: Description of thin section.

Figure Lithology
Description
ID Name
Euhedral halite with oscillatory zoning marked by fluid
P2f
Lower inclusion trails and clay particles. (PPL, 10x)
Halite Group of two-phase fluid inclusions with perfect cubic shape.
P1f
(PPL, 10x).
Fine grained kainite with small euhedral halite crystals. (PPL,
P1e
Kainitite 4x).
Unit Fine grained kainite with small euhedral halite crustals.
P2e
(XPL, 4x).
Primary bedding marked by fine- and medium- grained
P1d Lower
carnallite with mainly euhedral halite crystals. (PPL, 10x).
Carnallitite
unit Large carnallite crystal in thinly bedded carnallite halite
P2d
groundmass (XPL, 10x).
Finegrained bischofite with large amount of halite showing
P1c
Bischofitite irregular primary bedding. (PPL, 4x).
unit Fine grained bischofite with large amount of halite showing
P2c
irregular primary bedding. (XPL, 4x).
Thinly bedded primary carnallite with minor secondary
P1b carnallite in thin veinlets parallel to the bedding planes. (PPL,
Upper
4x).
Carnallitite
Thinly bedded primary carnallite with minor secondary
unit
P2b carnallite in thin veinlets parallel to the bedding planes. (XPL,
4x).
Coarse grained irregular sylvite with irregular randomly
P1a
Sylvinite distributed fluid inclusions. (PPL, 10x).
unit Coarse grained irregular sylvite with irregular randomly
P2a
distributed fluid inclusions. (XPL, 10x).

7.6 Schematic Model of the Danakil Depression

The source of lithium concentration in the Danakil depression is best summarized in
the generalized model (Fig. 7.9). The lithium is essentially concentrated by the
discharge of hydrothermal hot springs and the source of the lithium can be deep
cycling of meteoric or juvenile water that can interact with the country rocks to leach
the lithium and other ions. The second source of lithium could be through the
infiltration of sea water and subsequent evaporation. Lithium is being accumulated in
the residual brine. Hydrothermal activity and secondary leaching or replacement can
give rise for the depletion and enrichment of lithium in different evaporite horizons.
The third possible source for the accumulation of lithium may be the influx of surface
runoff water into the basin from the western and eastern escarpments. The model of
the Danakil show features similar with the generalized USGS model (Bradley et al.,
2013) for the formation of lithium brine deposits. The favorable situation for the
70
formation lithium brine deposit in the world includes arid climate condition, closed
basin containing a salar, tectonically driven subsidence, associated igneous or
geothermal activity, suitable lithium source-rocks, one or more adequate aquifers, and
sufficient time to concentrate the brine.

The Danakil Depression is characterized by extreme hydrothermal activity with

potash occurrences related to rift magmatism, marine flooding, and deep brine cycling
(Warren, 2016). Deposition of evaporite sequences in the Danakil area started late
Tertiary and continuing till today. Volcanism of mafic and felsic chemistry and
associated hydrothermal activity also contributed significantly to the geology of the
Danakil. Marine sediments including evaporites were deposited during late Tertiary
and early quaternary time by seawater infiltration from the Red Sea. The connection
to the Red Sea is capably blocked by the Danakil Alps, but sea water infiltration due
to the low elevation below sea level may be possible. The Danakil depression is
basically fed or filled by surface run-off water from the both side of the western and
eastern escarpments.

Figure 7. 9: Schematic Model of the Danakil depression for lithium occurrence.

71
 CHAPTER EIGHT

8.0 Conclusion and Recommendation

8.1 Conclusion/ Interpretation

A combination of field visits and geochemical analysis provides new perception about
the indication for the presence and absence of potential lithium brine and associated
evaporite deposits in the MER lakes and Danakil depression, mainly the Dallol area.
The geochemical result of the brines from the MER lakes are in the range of average
natural water lithium contents from <0.04 -0.54 ppm. In comparison brines from the
Danakil depression show much higher lithium concentration compared with the MER
lakes. The lithium concentration from the surrounding of Dallol surface brine ranges
1.9 to 9.8 ppm, lake Afdera 1 to 9.8 ppm and hot spring samples from mount Dallol
have lithium concentration 16 (20) ppm.

The geochemistry of the evaporite rock samples from the potash horizon suggests, on
Bore Hole 2, elevated lithium concentration was recorded on the upper and lower
carnallitite units (20 ppm) and BH 1 shows the highest Li- concentration in the
Bischofitite unit (40 ppm), but which is not a potash bearing horizon.

The analytical work of this research indicates the presence of elevated lithium content
in various surface brines, as well as in selected horizons of the tertiary-quaternary
evaporite sequence of the Danakil. The possible source of lithium concentration in the
Danakil depression is best summarized in the generalized model in Figure 7.9.

Deposition of evaporite sequences in the Danakil area started late Tertiary and is
continuing in varying intensity till today. Volcanism of mafic and felsic chemistry and
associated hydrothermal activity also contributed significantly to the geology of the
Danakil. Marine sediments including evaporites were deposited during late Tertiary
and early quaternary time by seawater incursion from the Red Sea. The connection to
the Red Sea is efficiently blocked nowadays and the Danakil depression is essentially
filled by surface run-off from the Western and Eastern escarpments. Sea water
infiltration due to the low elevation below sea level may be possible.

Three main sources of lithium in the brines and rock sequences of the Danakil are
displayed (Fig. 7.9). A. Hot springs show elevated Li, K, Mg values together with a

72
low Ca value. The source of those hydrothermal waters can be the result of deep brine
cycling due to heated and leaching meteoric waters, or juvenile waters associated with
the volcanic activity. Probably both water types are present in the Danakil but the
current work cannot distinguish between the meteoric and juvenile components. B.
During early quaternary sea water incursion and subsequent closed basin evaporation
lithium is concentrated during the precipitation of the K-and Mg-chloride phases
indicated by Li elevation in the Carnallitite and Bischofitite layers. This is in
accordance with the common lithium accumulation in evaporating sea water until the
stage of K-, and Mg-salt precipitation (Babel & Schreiber, 2014). C. Possible lithium
influx into the closed basin through annual surface run-off from the highlands mainly
west of the main rift escarpment, but also from the Danakil Alps in the East.

Even though the lithium concentration was low in the potash bearing evaporite
horizon 20 (40) ppm, the values can reach levels which may be of economic interests
in combined Potash and lithium extraction. During the pilot test of the potash, the
lithium concentration should be checked in different test ponds to see the variation.
The production of lithium does not need the construction of other processing plant
and it minimizes the cost and it only needs evaporation of the end brines and
separation of lithium from the other elements.

73
 8.2 Recommendations
 The lithium concentration in the MER lakes are low, but the unusual
geothermal brines and hot spring were not sampled from the MER so further
sampling and investigation for a better understanding of lithium distribution in
the rift is necessary.
 The enriched values of lithium from the Danakil depression validate additional
detail investigation and sampling for further assessment of the lithium
potential in the country.
 To understand further the genesis of the lithium bearing brines it requires
detailed studies of the brines using isotopic data.
 The elevated lithium concentration from the Danakil potash bearing evaporite
horizon warrants systematic drill core sampling, detail geochemical and
petrological investigation for the occurrence of lithium within the region.
 An extension of the current work to further drill core samples from the
Danakil depression which allows an interpretation of the spatial variation of
the lithium concentration is recommended to better understand the lithium
occurrence in the Danakil.
 The complex mode of formation of the Danakil evaporite sequence as
(Warren, 2016; Holwerda and Hutchinson 1968) needs more detailed
investigation for a conclusive interpretation of the Li-occurrence in the
Danakil depression.
 Extraction of lithium from the Danakil depression alone is currently not
possible economically but the potash companies are recommended to take the
end brine after the production of the potash and finally use the lithium
extraction techniques to use the lithium as a byproduct.
 A detailed look in to the possibility of developing low cost lithium extraction
method for brines associated with the solution mining of potash deposits in the
Danakil is recommended.

74
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