Advances in Geological and Geotechnical Engineering Research

Editor-in-Chief
Prof. Sayed Hemeda

Geotechnical Engineering and Architectural Preservation of historic buildings, Conservation Department, faculty of
archaeology, Cairo university., Egypt
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Amin Beiranvand Pour
Universiti Malaysia Terengganu, Malaysia
Editorial Board Members
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Volume 4 Issue 2 · April 2022· ISSN 2810-9384 (Online)
Advances in Geological
and Geotechnical
Engineering Research
Editor-in-Chief
Prof. Sayed Hemeda
Volume 4 ｜ Issue 2 ｜ April 2022 ｜ Page1-57
Advances in Geological and Geotechnical Engineering Research
Contents
Articles
1 Investigation of Miocene Methane Hydrate Generation Potential in the Transylvanian Basin, Romania
Unger, Z LeClair, D Györfi, I
9 Integrated Hydrogeochemical Analysis of Stream Water in Parts of Proterozoic Shillong Basin Megha-
laya, India
A.P. Dhurandhar
31 Understanding Contributions of Divalent Cations in Mineral Carbonation Using Artificial Neural Net-
work
Abidoye, L.K Oladipo, H.B
37 Assessment of Geotechnical Properties of Laki Limestone for Coarse Aggregate, Nooriabad, Jamshoro
Sindh, Pakistan
Sumaira Asif Khan Adnan Khan
48 A Typical Sublithospheric Mantle beneath the Tello Region, SE-Ngaoundéré (Cameroon Line)
Nguihdama Dagwai Kamgang Pierre Mbowou Gbambié Isaac Bertrand Chazot Gilles Ngounouno Ismaïla
Advances in Geological and Geotechnical Engineering Research | Volume 04 | Issue 02 | April 2022

https://ojs.bilpublishing.com/index.php/agger
ARTICLE
Investigation of Miocene Methane Hydrate Generation Potential in
the Transylvanian Basin, Romania
Unger, Z.1,2* LeClair, D.2 Györfi, I.3
1. ELTE University, Szombathely, Hungary
2. Oil & Gas Development Central Kft., Budapest, Hungary
3. RomGaz, Târgu Mureș, Romania
ARTICLE INFO ABSTRACT
Article history In geology we often revise theoretical models; upon finding new evidence,
Received: 27 January 2022 such as the discovery of methane hydrates, the initial model will be
challenged immediately. Hereby the authors put forward two postulates:
Revised: 08 March 2022 1) There is a third, previously unexplored source of methane in the
Accepted: 15 March 2022 Transylvanian Basin, based on a new theoretical approach on methane
Published Online: 01 April 2022 hydrate formation; 2) The dissociation of methane hydrates creates a strong
chlorinity anomaly. Based on a recent analogy with the Black Sea basin
Keywords: model, we apply our statements to the Transylvanian Basin. Using direct
and indirect indicators and the published system tract analysis, we claim
Deep hypersaline anoxic basin that there are substantial grounds to believe that this model of methane
Methane hydrates hydrate formation applies to the Miocene Transylvanian Basin. Due to
Methane hydrate dissociation the increase of the geothermal gradient as a result of the volcanic activity
from the Eastern Carpathians, the clathrates dissociated into methane
Chlorinity anomaly
and freshwater. This process of dilution resulted in a chlorinity anomaly
that can be spotted in the formation waters of several gas fields from the
Transylvanian Basin.
1. Introduction It was the potential of discovering potassium salt (sylvine)

that attracted the geologists to this region [1] - and indeed,
The Transylvanian Basin (TB, Romania) is situated
they found dry gas.
in the eastern part of the Carpathian Basin (Figure 1)
between the Eastern Carpathian and Apuseni Mountains, The complicated geological build and evolution of the
and between the Southern Carpathian and Maramureș Transylvanian Basin is well documented in several recent
Mountains. As an important hydrocarbon province, it has publications [2-8].
been the target of constant exploration in the last century. The Transylvanian Miocene sedimentary basin, with its
*Corresponding Author:
Unger, Z.,
ELTE University, Szombathely, Hungary; Oil & Gas Development Central Kft., Budapest, Hungary;
Email: zunger21@gmail.com; unger.zoltan@sek.elte.hu
DOI: https://doi.org/10.30564/agger.v4i2.4413
Copyright © 2022 by the author(s). Published by Bilingual Publishing Co. This is an open access article under the Creative Commons
Attribution-NonCommercial 4.0 International (CC BY-NC 4.0) License. (https://creativecommons.org/licenses/by-nc/4.0/).
1
thick lithosphere [7], was part of the Central Paratethys and representing analogies for the present Mediterranean
is regarded as a cold piggyback basin. This contrasts with DHAB [6,17]. These brines can have ~70 mg/L biogenic
the Pannonian Basin, with its thin lithosphere and elevated methane [21].
thermic gradient. In the present article the authors outline a possible third
methane source for the Transylvanian gas reserves. We
consider that the methane hydrate research of the current
Black Sea basin [12,13] provides a perfect analogy with
methane hydrate generation during the Miocene in the
Transylvanian Basin.
2. Methods and Materials

Examining some of the special literature records
with a critical eye, we describe a theoretical approach to
the existence of a potential third source of methane in
the Transylvanian Basin. This idea is supported by the
Figure 1. Location of the Transylvanian Basin - Romania formation waters of the Badenian gas reservoirs.
The Transylvanian Basin hosts important gas reserves 2.1 The Origin of Methane in the Transylvanian
in the post-salt deposits with characteristic salt tectonics, Basin
studied by several researchers [2-5,7-11]. The origin of the
pure methane reserves is a matter of standing debate, The Transylvanian Basin has a thick lithosphere, and
since the sheer amount of methane and the volume of it is considered a so-called cold sedimentary basin with
methane production suggests the presence of a secondary huge salt deposits. The filling deposits of the post-salt
gas source, in addition to the classical biogenic source [17]. basin solely trapped biogenic dry gas [4], but the volume
The industrial gas reserves were discovered by the of gas generated strongly exceeds the expected average.
Kissármás-2 new-field wildcat, although the drilling was As a recent analogy, the Black Sea basin contains an
initially designed for sylvine exploration [1]. This was the elevated amount of dissolved methane: 96 Tg. This is 2.4-
starting point of the exploration for the most important 6 times larger than the global annual geological methane
biogenic gas province (99% methane) from the Carpathian contribution to the atmosphere [14]. In the last more than
Basin, which still continues to produce gas. As a rough ten years, the increasing number of gas flux measurements
estimate: 30-35 TCF gas was produced from 90 fields in puts the methane emissions between 30-76 Tg/y [22], which
the last 100 years [18]. Being the focus of research efforts, is roughly the same range as the dissolved gas mentioned
the basin has undergone intensive exploration in the above.
last few decades in order to understand the hydrocarbon These make the (formerly sedimentary) Transylvanian
system. Various interpretations and analyses were run and Basin and the Black Sea basin an interesting and attractive
published by several research groups, confirming that the target to explore the origin of gas accumulation.
Transylvanian Basin is a mature basin. One of the main Crânganu & Deming’s thermal modelling of the
results came from Krézsek Cs., Filipescu S., Silye L., Transylvanian Basin [15] proves that the oil window is under
Matento L., Coltoi O. etc. and co-authors [2-5,7-11]. the salt horizon; as a result, the methane trapped in the
The post salt deposits contain the traps, mostly 4-way post-salt reservoirs can have exclusively biogenic origins.
closures related to the salt-cored folds [19]. The reservoirs It is obvious that low heat flow (average 45 mW/m 2)
are composed of Late Badenian to Late Sarmatian means immature post-salt deposits [15].
siliciclastic deposits with good porosity (~20%) and This potential origin will be confirmed when recent
permeability (<1 D) sealed by argillaceous intercalation. isotopic measurements become available [4]. Similar
The biogenic gases are primarily considered to isotopic measurements have shown that the hydrates in
originate in low quality transgressive deep marine shales the Black Sea have microbial origin, with methane δ13C
with TOC ~1%, in which the organic material is thermally values of −84‰ to −70‰ and concentrations of 99.1%-
immature [15,20]. 99.9% [16]. We expect similar values for the Transylvanian
Deep Hypersaline Anoxic Brines (DHABs) are con- Basin’s gas isotopic analysis.
sidered to be a second source of Transylvanian biogenic This allows for the presumption that the local methane
methane, which could be formed in the Middle Miocene, could have multiple sources [17]. Besides the well-known,
2
classical biodegradation of organic matter from the post-

salt sedimentary sequence, we suppose the existence of
a secondary methane source. These are the ancient Deep
Hypersaline Anoxic Basins (DHAB) from the Middle
Miocene in the Transylvanian Basin, where a considerable
amount of methane could be produced by bacteria [6,23].
A modern analogy for such DHABs has recently been
described in several places around the globe; one of the first
[24]
being the Mediterranean Range . An important feature
of these layered brines is that they host methane generated
[25]
by bacteria . Methane in these brines can amount
[21]
Figure 2. Hydrate formation and stability zones in the
to ~70 mg/L concentration . Similar ancient brines can Black Sea basin
be considered secondary methane sources for sedimentary (after Radu Gh. & Sandu V., 2015)
basins, i.e. the Miocene Transylvanian Basin [17].
Based on the system tract analysis for the Miocene
2.2 Recent Methane Hydrate Facies - Analogies sedimentary Transylvanian Basin by Krézsek et al. [4], it
for the Miocene Transylvanian Basin was shown that gas hydrate stability zone started at ~400
m seawater depth in deep lacustrine environments, at
In earlier decades the American and Asian methane least up until the Sarmatian age. As a consequence, the
hydrates represented the focus of hydrate exploration, probability of methane hydrate formation was high over a
[13]
but Minsull et al. recently edited a review about the relatively long period, approximately ~4 MA.
methane hydrate potential of Europe. They defined (direct If we apply Minsull’s direct and indirect hydrate
and indirect) hydrate indicators in order to delineate indicators [13] to the Miocene Transylvanian Basin, we
find several overlaps with the actual Black Sea basin
a restricted exploration acreage, and the drilling cores
indicators. We are aware that the identification of similar
subsequently proved the existence of methane hydrate.
Miocene direct indicators is troublesome; however, it is
One such successful area of exploration was the Black known that gas seepages and chlorinity anomalies are
Sea basin. present as indirect indicators. From among the indirect
If we look for the current methane hydrate generation indicators, we highlight the subsurface escape structures
facies, the perfect analogy for the Transylvanian Basin and gas escapes of mud volcanoes active in our days
is the Black Sea. This theory is supported by Radu & (Figure 3) [28].
Sandu [26], who published an article on gas hydrate stability
(GHS) in the Black Sea. Figure 2 depicts the methane
hydrate stability zones based on drillings in the seafloor
sediments. This figure explains how the temperature
and phase curves outline two GH stability zones: one
between 400 m-770 m, and the second between 1,000
m-1,600 m. According to the above mentioned authors, Figure 3. An active mud volcano at Homoród, with a
more than 10 methane hydrate horizons are documented well-expressed flat cone, small crater and mud flows: (a)
in the sedimentary deposits between 400 m-800m under general view, (b) detail of the cone
the seafloor. This idea is also supported by Zander (Photo by Silviu Rădan courtesy to Seghedi et al. [28])
[12]
et al. , examining a seismic cross section to highlight
We overlaid the mud volcano database on a lineament
the characteristic bottom simulator reflectors (BSR) in
map generated from the digital terrain model [29]. The
the offshore regions of the Danube Delta. Furthermore, distribution of the mud volcano structures shows a perfect
[27]
Vassilev & Dimitrov propose that 91% of the seafloor overlap on the lineaments of the Transylvanian Basin
is within the range of the gas hydrate stability zone. (Figure 4) [30].
3
the escaped methane molecules can be caught in hydrate

cages.
In the case of the actual deep hypersaline anoxic brines
in the Mediterranean Range it was shown (and even
measured) that the brines produce a methane output [24]
(Figure 5).
Figure 5. Measuring the daily methane output with a

mobile mass spectrometer
(courtesy to MedRIFF 1995)
In Table 1, Yakimov et al. [21] compiled the average

chemical composition of the Medee Lake brine from the
Figure 4. Relationship between mud volcanoes and
lineaments [29] Mediterranean Basin. The layered brine has varying build-
up and composition structure, and it clearly shows the
In 2010 Spulber et al. measured 27 gas flux sites out of methane content and salinity (blue lines), as well as the
the 73 documented mud volcanoes in the Transylvanian
daily methane production MPR (red line).
Basin, and extrapolated that the methane output could be
This is a possible analogy for the methane output from
up to 680 t/year [31].
the ancient brines (DHAB) within the Miocene Transyl-
These indirect indicators represent arguments for the
vanian Basin. Without making quantitative assumptions
existence of Miocene methane hydrates.
(which would require further detailed modelling and
The huge trapped methane reserves lead us to presume
analysis), we can state that it is highly probable that con-
that methane in the Transylvanian Basin might have
siderable methane output was released from the Miocene
multiple sources [17].
brines in the Transylvanian Basin [6].
Up until now the classic sedimentary deposit sequence,
rich in organic matter, has been considered the primary 2.4 Theoretical Approach for Methane Hydrate
and sole source of biogenic methane in the Transylvanian Formation in the Transylvanian Basin
Basin. However, recent analogies have shown that ancient
DHABs can be considered as a secondary source, with Based on the actual methane output from the brines
biogenic methane concentrations as high as ~70 mg/L [21,25]. and using these as an analogy for the ancient brines from
We propose that dissociated methane hydrates can be geological times, the question emerges naturally: what is
regarded as a third source of methane, formed in the deep happening with the escaping methane molecules?
lacustrine environments from the Middle Badenian up In accordance with the thermodynamic potential, in a
until the Late Sarmatian age. cold basin the escaped methane molecules will be frozen
and caught by water molecule clathrates, forming methane
2.3 Miocene Methane Hydrates Formed in the
hydrates (MH). The salty seawater presents an obstacle in
Transylvanian Basin
this process. Figure 6 shows methane hydrate stability in a
As mentioned above, the methane component of coordinate system, depicting temperature versus pressure
methane hydrates can originate from DHABs, as well as in the presence of NaCl. The different colours correspond
from the normal bacterial degradation of organic matter. to increasing rates of salinity concentration from 1 mol to
Under the appropriate marine thermodynamic conditions, 5 mol.
4
Table 1. Average chemical composition of the Medee Lake brine
hydrate freezes.
This process of methane hydrate generation can be
repeated for as long as methane production is active and
the thermodynamic conditions stay unchanged. The ice
clathrates can be preserved for geological times on the
bottom of the basin in the gas hydrate stability zone,
where further methane hydrates could accumulate as the
basin fills up. In the case of the Transylvanian Basin this
took place on the deep lacustrine facies from the Late
Badenian to the Late Sarmatian period.
Figure 6. Methane hydrate stability in the presence of
NaCl [mol] (P-T diagram)
The lowest curve (dark blue) shows a seawater
concentration of 35 mg/L = 0.59 mol. The diagram
demonstrates that methane hydrate stability is more
sensitive to temperature than to pressure in normal
seawater. The curve is almost parallel to the temperature
axis. The importance of this is highlighted when the
freshwater output from the brines [6] dilutes the normal
seawater concentration. This will immediately facilitate
the formation of methane hydrate, i.e. water freezing
together with the methane. Figure 7 sketches out the
process:
(1) The brine pool releases fresh water and dissolved
methane into the normal seawater [6]; Figure 7. The interface process between seawater
(2) This will dilute the seawater, reducing the salt and brine: beyond a certain pressure and at a certain
concentration to levels under 35 mg/L=0.59 mol, which temperature, the brine releases water and methane into
eliminates the obstacle (salty water) to form methane normal seawater. This dilutes seawater and facilitates
hydrate; methane hydrate generation.
(3) Due to the thermodynamic potential, the methane (MedRIFF 1995 figure amended by the authors)
5
3. Discussion Our deduction is: besides the primary and secondary

methane sources, there is a tertiary methane source:
3.1 Recent Chlorinity Anomalies Generated by dissociating methane hydrates. The exclusively dry gas
Ancient Methane Hydrates (the absence of the thermogenic methane) shows that only
Once the volcanic activity started in the Eastern biogenic methane was trapped in the reservoirs from those
Carpathian, the regional geothermal gradient increased, three sources.
and the trapped methane hydrates started to dissociate. It
4. Conclusions
is also well known that: 1 m3 MH yields 0.8 m3 freshwater
and 164 m3 CH4 [32]. The authors attempted to draw an analogy between
This process triggers considerable volume increase the current methane hydrate occurrence in the Black Sea
and creates an overpressure zone. Due to this pressure, basin and the possible methane hydrate formation in the
methane starts migrating to the reservoirs and traps. The Miocene Transylvanian Basin deposits. The analysis of the
melted freshwater generated by dissociation dilutes the direct and indirect indicators suggests that all conditions
reservoir water, reducing its initial salinity. Consequently, supporting the formation of methane hydrate exist in the
the chlorinity anomaly indicator is present. Miocene Transylvanian Basin.
In the case of the Transylvanian Basin, the initial reservoir The relatively high frequency of active and less active
waters of 120-200 g/L salinity will be diluted. This is the mud volcanoes - as indirect indicators - represent a strong
reason why formation water reaches salt concentration levels argument for the existence of former methane hydrates.
between 7-12 g/L, thus creating a strong chlorinity anomaly. The methane, generated from the primary (biodegra-
This phenomenon occurs frequently in the Transylvanian dation) and the secondary (DHAB) sources, was trapped
Basin (Figure 8) and it is mostly characteristic of deep in water clathrates, creating multiple Miocene meth-
reservoirs related to gas fields such as: ane hydrate horizons, similarly to the Black Sea today.
Grebenișu de Câmpie (7-18 g/L), According to the water depth, in a cold sedimentary basin
Dobra (3-15 g/L), (such as the Miocene Transylvanian Basin), the required
Corunca North (11-12 g/L), thermodynamic potential was present for the generation
Corunca South (9-20 g/L), of methane hydrate. This phenomenon lasted from the
Filitelnic (1-13 g/L), Middle Miocene until the Late Sarmatian age over a
Magherani (7-19 g/L), period of ~ 4 MA.
Damieni (8-20 g/L), Those methane hydrates could have been preserved for
Eremieni (5-17 g/L), millions of years until the Eastern Carpathian magmatic
Lechința (5-20 g/L), activity started, when the regional geothermal gradient
Luduș (3-21 g/L), increased, and the methane hydrate consequently
Șincai (7-17 g/L), dissociated. This melting yielded free methane, which
Laslău Mare (3-15 g/L), escaped from the H 2O molecule clathrate cages. The
Deleni-Hărănglab (1-27g/L) [33]. remaining freshwater, now made up of pure H 2 O
molecules, is responsible for the low salinity of the
formation water, i.e. the normal reservoir salinity was
diluted by the melted hydrates, creating the chlorinity
anomaly. 1 m3 MH yields 0.8 m3 freshwater and 164 m3
CH4.
This idea is supported by the low salinity concentration
(7-12 g/L) of the formation waters of several gas fields in
the Transylvanian Basin.
Based on these theoretical considerations we can state
that:
1) The dry gas in the Transylvanian Basin can have a
tertiary source. The generated gases could have initially
been trapped as methane hydrate, just like in the current
Figure 8. Chlorinity anomalies (g/L) for the dry gas fields Black Sea basin.
in the Transylvanian Basin 2) After dissociation the methane migrated into traps
(Basemap courtesy of IHS) formed by salt tectonics, and the resulting melted water
6
diluted the formation water. and Petroleum Geology. 27, 191-214.

This hypothesis urges us to re-evaluate the origin of DOI: https://doi.org/10.1016/j.marpetgeo.2009.
methane wherever the salinity level of reservoir waters 07.009
has dropped, wherever it may be on the globe. [5] Mațenco, L., Krézsek, Cs., Merten, S., et al., 2010.
Characteristics of collisional orogens with low topo-
Author Contributions graphic build-up: an example from the Carpathians,
The authors have the following contribution to this Terra Nova. 22, 155-165.
article: Unger: 40%, LeClair: 40%, Györfi: 20%. DOI: https://doi.org/10.1111/j.1365-3121.2010.
00931.x
Conflict of Interest [6] Unger, Z., LeClair, D., 2018. Salt and Methane Gen-
eration Initiated by Membrane Polarisation. Earth
The authors have no conflicts of interest. Sciences. 7(2), 53-57.
DOI: https://doi:10.11648/j.earth.20180702.12
Funding
[7] Tiliță, M., Lenkey, L., Mațenco, L., et al., 2006.
The research of the project entitled Parallel Salt and Neogene evolution of Transylvania basin: insights
Methane Generation was supported by the Oil&Gas derived from (2D steady-state) thermal modelling.
Development Central Ltd. Hungary and Sandhill Geophysical Research Abstracts. 8, 08874. SRef-ID:
Petroleum Romania Ltd. This article is an integral part of 1607-7962/gra/EGU06-A-08874.
the project. [8] Tămaş, D.T., Schléder, Zs., Krézsek, Cs., et al., 2018.
Understanding salt in orogenic settings: The evolu-
Acknowledgements tion of ideas in the Romanian Carpathians, AAPG
This work was supported by Oil&Gas Development Bulletin. 102(6), 941-958.
DOI: https://doi.org/10.1306/0913171615517088
Central (O&GD C.) Ltd. Hungary. We express special
[9] Böckh, J., 1911. Notes about the anticlines with gas
thanks to Mr. Pete NOLAN (senior consultant) and Mr.
reserves from the Transylvanian Basin, Geological
David Westlund (Exploration Director at O&GD) for
Bulletin of the Hungarian Geological Society, Buda-
continuous discussion, encouraging support and essential
pest. XLI, 235-239. (in Hungarian)
expert advice.
[10] Paraschiv, D., 1979. Romanian Oil and Gas Fields,
We are grateful to the RomGaz company for providing
Studii Tehnice și Economice/Geological and Geo-
formation water salinity data. We express our gratitude to
physical Institute/Technical and Economic Studies.
our RomGaz colleagues for lending a critical ear to our
Seria A, Bucharest. 13, 382.
new hypotheses.
[11] Nemeșan, M., 2007. Romgaz. Present and Perspec-
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ical Congress, Oslo, Norwegia, 6-14. August, Pro-
2013. Microbial life in the Lake Medee, the largest
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deep-sea salt-saturated formation. Scientific Reports.
[31] Spulber, L., Etiope, G., Baciu, C., et al., 2010. Meth-
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[22] Etiope, G., Schwietzke, S., 2019. Global geological noes in Transylvania (Romania), Geofluids. 10, 463-
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8

ARTICLE
Integrated Hydrogeochemical Analysis of Stream Water in Parts of
Proterozoic Shillong Basin Meghalaya, India
A.P. Dhurandhar*
Katol Road, Nagpur, 440013, India
Article history Hydrogeochemical surveys were conducted in parts of the Proterozoic

Received: 08 March 2022 Shillong basin in Meghalaya to locate the unconformity-related uranium
deposits, related alteration patterns, and the influence of the rock
Revised: 11 April 2022 formations on the groundwater solute chemistry. Shillong Basin comprises
Accepted: 18 April 2022 Proterozoic metasediments and felsic volcanics of Tyrsad Formation,
Published Online: 25 April 2022 undeformed arenaceous Barapani Formation with intrusive granites, and
metabasic sills and dykes. The groundwater quality is determined for
Keywords: drinking, and domestic-agro-industrial utilities using hydrogeochemical
tools and physicochemical parameters. The water is acidic to slightly
Hydrogeochemistry alkaline and has an oxidizing redox environment, Electrical Conductivity
Water quality (EC), Total Dissolve Solids (TDS), and major ions fell below the World
Subsurface relations Health Organization (WHO) and Indian Standards Institute (ISI) acceptable
limits except for Zn, Fe, and SiO 2 showing higher concentrations.
Shillong basin
The sequences of abundance of major cations and trace elements are
Fe>Zn>SiO 2>Ca 2+>Na +>Mg 2+>K +>U and anions as HCO 3>Cl ->SO 42-.
Groundwater character was assessed by ion exchange, simple dissolution,
and unusual dissolution mechanisms. The area has dominant CaHCO 3,
NaHCO3, and restricted CaMgHCO3 type water. Plagioclase dissolution
and high SiO2 and cation exchange of Ca for Na were identified. The
groundwater indices of Sodium Percent, Kelley’s Index, Sodium Adsorption
Ratio, Magnesium Ratio, Electrical Conductivity, TDS, USSL, and Wilcox
index were found suitable for agro-industrial uses. Permeability Index is
found to be suitable in most areas and the Corrosivity Ratio shows the
areas of galvanized pipes and PVC pipes to be used for water supply. AHC
analysis shows three distinct groups of water types, as well as the factor
analysis, also shows the three prominent factors of water types defining the
dimensionality of water types. Magnesium metasomatic alteration zones
and Zn anomalous zones are delineated.
A.P. Dhurandhar,
Katol Road, Nagpur, 440013, India;
Email: apdhurandhar@gmail.com
9
1. Introduction Shillong basin.
The objective of the hydrogeochemical survey in the 2. Geology and Structures

present study is to explore the possibilities of Proterozoic
The surveyed area exposes Proterozoic lithologies
unconformity-related uranium deposits in Shillong
consisting of metasediments and volcanics of Tyrsad
Basin Meghalaya. Traditional mineral prospecting
Formation, undeformed arenaceous Barapani Formation
methods present an obstacle when applied to areas with
with intrusive granites, and metabasic sills and dykes
transported cover and very high gradient, especially
(Figure 1). The metasedimentary rocks of the Shillong
where the coverage is larger than a few meters thick, as in
group can be divided into two broad lithofacies [7], the
the Shillong basin. Groundwater, a geochemical sample
older argillaceous and the younger arenaceous. Tyrsad
that travels through the subsurface, is easy to collect and
Formation is a metasedimentary sequence consisting
can be evaluated with high sensitivity and precision. It
of phyllites to schistose units such as carbon phyllite/
presents a chemical fingerprint of mineralization due to
graphitic schist, phyllite/slate, chlorite schist, sericite
varying Eh-pH conditions, alteration, clay adsorption,
schist, chlorite-sericite schist, mica schist, and quartzite
and clays and hydrous metal oxides such as iron and
(Table 1). In the south of the NE-SW trending Umiam
manganese which can directly change the uranyl ions’
river chloritic phyllite and chlorite schist are the dominant
mobility and dispersal [1-3]. Groundwaters that drain
litho units while in the north of the Umiam river sericite
through various rock types like igneous, metamorphics,
schist and chlorite-sericite schist are the dominant litho
and sedimentary (felsic, alkali, basics) can also change the
units. Along the Nongpinom-Mawklot, Umlyngka
uranium concentration in groundwater and may give rise
tract carbon phyllite is exposed along the small river
to pseudo uranium anomalies. True uranium anomalies can
(rivulet) sections just below the conglomerate horizon,
be overlooked if the effect of local surface or rainwater
which invariably contains pyrites. Alteration features
dilution is not recognized. A regional ground-water study like chloritisation are intense in Tyrsad Formation
can indicate where target formations occur within the throughout the area and sericitization in the northern
economic range of the surface. Anthropogenic activities/ part along the Mawpun-Nongbsap tract. The volcanic
requirements such as mining activities and related component of the Tyrsad Formation consists of rhyolite,
pollution, and drinking water scarcity are major concerns intermediate volcanics, and quartz porphyry. Sheared
and hence necessitate water quality monitoring [4] . rhyolites are dominating the northern margin of the area.
The Shillong plateau is a high rainfall area but the The unconformity contact between Tyrsad and Barapani
nearby cities, towns, and villages mainly depend upon Formation is erosional and marked by the development
the rainwater, spring, and river water for drinking and of a thick conglomerate bed at the base of the Barapani
irrigation purposes. Due to stricter legislation on soil and Formation. The conglomerate is polymictic, clast
groundwater contamination and increasing population supported, and consists of pebbles of quartzite, quartz,
and demand in food production, Hydrogeochemistry and volcanic components derived from the underlying
is complex and needs to be evaluated in the context Tyrsad Formation. The pebbles are stretched and sheared
of bedrock geology, regolith development, regional and the matrix is schistose and foliated. Unconformity
groundwater flow, and anthropogenic disturbances before contact in the surveyed area is traced along the north of
assessing the effects of mineralization on the chemistry. Laitjem to the southeast of Lummwablei village. The
Major ion composition of groundwater is important as it Barapani Formation is an arenaceous sequence that rests
can identify water types, mixing, evaporation, water-rock unconformably above the metasediments and volcanics
interaction, and recharge of the particular groundwater of the Tyrsad Formation. It starts with a basal sheared
system. However, some studies have also suggested that conglomerate followed by pebbly arenite, coarse cream-
the major ion composition of groundwater can provide colored arenite, and whitish friable arenite showing a
direct vectors to mineralization, in particular owing to fining upward sequence north of Mawtawar village. The
the generally larger target provided by alteration halos arenites are cream to grey colored, medium to coarse-
around mineralization relative to the size of primary grained with argillaceous material as the matrix. Barapani
ore mineralization [4-6]. Hydrogeochemistry and water formation occupies a large part of the surveyed area. The
management in agriculture are aiming for better tools regional strike of the Shillong group of rocks is NE-SW
to estimate risk assessment. Water quality assessment is with alternate rolling dips and steep subvertical zones [7,8].
a major value-added by-product of such investigations. A shear zone extending from Tyrsad to Barapani (Figure
Such studies have never been carried out in parts of the 1b, 1c) was described based on slickensides [9-11]. The
10
regional sigmoidal pattern of the intraformational con-

glomerate broadly correlates with the Tyrsad-Bara-
pani Shear Zone (TBSZ) of sinistral nature. Barapani
Formation at places shows intense ferruginisation and
limonitisation (Umlyngka - Umiam river road section)
along the ENE-WSW, and NNE-SSW trending fracture.
Ferruginisation is intense at the intersection of these
two fractures. This ferruginisation and limonitisation
processes indicate extensive oxidation in Barapani arenite.
Argillisation is also observed in the axial portion of the
folded Barapani arenite along the Nongumlong-Umiam,
and Lummawsiang-Umsaw road section. Sedimentary
structures such as current bedding, cross-bedding, and
graded bedding are well preserved in the Barapani
Formation. In the surveyed area Neoproterozoic to early 1c.
Paleozoic granites such as Mylliem granite (607±13 Ma), Figure 1. 1a: Geological map of the study area.
and Kyrdem granite (479±26 Ma) intrude the rocks of the 1b: Satellite Image of the study. 1c: Shuttle Radar
Barapani Formation with sharp intrusive contact [12,13]. The Topographic Mission (SRTM) data of the study area.
amphibolites and metadolerites intrudes both Barapani
and Tyrsad Formations as sills and dykes, showing NE- Table 1. Lithostratigraphic succession of the study area.
SW to ENE-WSW trend. Metadoleritic dykes of both Era Formation Lithology
fresh and sheared nature are observed in this area (Um Late ProterozoicKyrdem Granite
Ban rivulet, Nongumlong-Umiam river road section, N of Coarse, porphyritic grey, and
(479±26Ma)
pink granites Zircon ages of 430-
Laitjem-Mawkrih-Nongpinom). Early Palaeozoic Mylliem Granite
480 and 500Ma
(607±13Ma)
Intrusive contct
Metabasic Sheared meta-doleritic sills and

intrusives dykes
Intrusive contact
Cream colored, current and

X
Y
cross-bedded,
Meso- Barapani Quartz arenite (> 560-Ma
Proterozoic Formation detrital zircons) with shaly
X Y
intercalations, Pebbly and gritty
arenite(±pyrites),
1a.
Sheared, stretched, clast supported Polymictic conglomerate
Rhyolite, intermediate volcanics

Carbon phyllite/Graphitic schist
(pyrites)
Phyllite/Slate, Chlorite schist,
Palaeo- Tyrsad
Sericite schist
Proterozoic Formation
Chlorite sericite schist, mica
schist
Quartzite (>1100 Ma detrital
zircon)
Unconformity
Basement gneissic complex not exposed (1100 to 1650 Ma based on
Zircon dates)
[10,11]
N.B. Kyrdem and Mylliem Granite Rb-Sr dates after , and
1b. Zircon ages are after [16].
11
Structural Setting associated with retrograde greenschist facies of metamor-

The Proterozoic litho units of the surveyed area show phism, which is indicated by the growth of axial planer
a regional foliation of NE-SW to ENE-WSW with 40° to biotite and chlorite and chloritization of garnet. Integrated
subvertical dips SE-SSE in Tyrsad Formation and 10° to structural and geochronological investigations reveal that
25° SE, SSE in Barapani Formation. The structural history the Shillong plateau has been affected by four phases of
of the rocks of Shillong Group in the study area depicts magmatism at ca. 1600 Ma, ca. 1100 Ma, ca. 500 Ma,
four phases of deformation; viz: a sub-horizontal simple and ca. 105 Ma-95 Ma, and four episodes of deformation
shear in NW-SE direction acting on horizontal beds gave at 1100 Ma, 500 Ma, 100 Ma, and 20 Ma-0 Ma have
rise to recumbent, isoclinal F1 fold with NE-SW axial been documented [17]. This analysis suggests that the
trend. The F2 folds have developed when simple shear intrusive granites and Augen gneisses contain inherited
gave way to pure shear with NW-SE compression so that zircon dating 1600 Ma-1100 Ma and the second phase of
upright folds with NNE axial trend resulted, rotating the granites contains 520 Ma-430 Ma zircon which means the
axial planes of F1 folds coaxially with the development of Shillong group of rocks i.e., sandstone and shale upper
crenulation cleavage [14,15]. The F3 folds developed locally part contains > 560-Ma detrital zircons, and the lower part
due to maximum compression in vertical to subvertical contains >1100 Ma detrital zircon. The sequence (Shillong
thinly layered rocks so that there is continuity in the first group) is intruded by 520 Ma-480 Ma granitoids and
three stages of deformation which is revealed by these isoclinal foldings and concomitant deformations in the
three sets of coaxial folds. The F4 folds are open warps Shillong group have occurred between 520 Ma to 500 Ma
with different axial trends E-W, N-S, NW-SE, developed (Age of the two deformations due to granitic intrusions).
entirely in a different pattern by horizontal compression
Image Linea
355
350
345
in a NE-SW direction in the last stage of deformational
10
0
5
15
340
20
335
Calculation Meth
25
330
episode equally supported by the lineament rose diagram
30
32 6 Class Interval .
35
5
32 5
40
(Figure 2). The lithostructural mapping was also carried
0
Length Filtering
31
31 5
45
0 50 Azimuth Filterin
out using satellite images namely Landsat 8 OLI and 30
30
5 4 55
0 60
Data Type ......
Sentinel 2 data in conjunction with the SRTM digital 295
3 65 Population .....
terrain models (Figure 1b and 1c). The F4 structures, 290
2
70 Maximum Percenta
285 75 Mean Percentage
therefore, furnish evidence of longitudinal shortening in 280 80
1 Standard Deviati
the final stage of deformation Umlyngka-Umiam river 275 85
Vector Mean ....
270 6 5 4 3 2 1 1 2 3 4 5 6 90
road section. NE-SW trending Tyrsad-Barapani shear zone 265 95
Confidence Inter
is characterized by: 260
1
100 R-mag ..........
105
i. Drastic reduction in grain size of the country 255 2
110
250
rocks. 245
3 115
0 12
ii. Intense silicification. 24
5
4 12
0
23 13
5
iii. Development of hydrous phases of mineral and 23
0
5 0
5
13
incipient gossans.
22
5
0
14
22
6
0
5
14
21
iv. The regional sigmoidal pattern of the intraform-

210
150
5
205
155
200
160
195
165
190
170
185
180 175
ational conglomerate broadly correlates with the Tyr-

sad-Barapani Shear Zone (TBSZ) of sinistral nature [14].
N= 447
In the surveyed area this shear zone is manifested by the
Vector mean =55.98°N
presence of sheared conglomerate, slickensides / striated
Figure 2. Lineament Rose diagram for Shillong Basin
limbs of F1 folds in chloritic phyllite, altered basic rocks,
and NE - SW trending ridges [15,16].
3. Geomorphology and Hydrogeology
In Barapani Formation, folds are of the open type
with NE-SW axial trend. The NNE-SSW & ENE-WSW Geomorphologically the area shows a moderately
trending fractures are common. Tyrsad Formation has dissected hill (Northern part) and dissected Plateau
been affected by three distinct phases of deformation in the southern part. The dissection of these areas is
while the Barapani Formation has been subjected to mainly due to lineament-controlled drainage systems.
only the last two phases of deformation thus suggesting The dominant trend of lineaments in the Shillong basin
younger age. Intense deformation led to recrystallization is NNE-SSW. In the central part of the Shillong basin,
corresponding to a higher almandine-amphibolite grade the crystalline and metasedimentaries are peneplained
of metamorphism [15,16]. The second deformation phase is to gently sloping surfaces and are grouped in dissected
12
Plateaux. The dissection in the central part still preserves 4. Materials and Methodology
the old plateaux characters. Lineament-controlled
A total of 108 water samples were collected from the 1st
drainage patterns with patches of sub-dendritic drainage
and 2 nd order streams draining in the survey area of
characterize the area. In NE-SW trending fault zones,
175 km 2 with a sampling density of 1:1.62 km 2. The
escarpments are common. Lineaments are either straight
stream and spring water sampling was done during the
or curvilinear in NNE-SSW directions [18].
post-monsoon period (November-January) when stream
The temperature ranges from 1.7 °C to 24 °C, and the
flows remain constant. The sampling was suspended
climate ranges from temperate humid to subtropical hu-
during the storm runoff periods after the heavy rains in the
mid. The area receives very high rainfall, the rainy season
area. The water table is dissected by topography giving
is from April to October, though none of the months is
rise to several springs in the survey area. The samples
completely dry. December’s driest month, with 19 mm (0.7
were collected from such springs after a few tens of
inches) of rainfall. Most of the precipitation here falls in
meters of surface flow. The data collection methods are
July, averaging 714 mm (28.1 inches). The months with
similar to standard hydrogeochemical sampling methods
the greatest temperatures are also those with the wettest described by Brown and Woods et al. [22,23]. However,
weather, making the environment humid [19]. The northern appropriate quality assurance (QA) and quality control
areas of Shillong are also distinguished by the existence (QC) measures were performed during sample collection
of a variety of rivers, including the Umtrew, Umiam, and analysis. Data screening and duplicate removal were
and Umkhen. The Brahmaputra River is fed by rivers in carried out before processing. The Total Dissolved Solids
the northern section of the area. The Quartzite deposit of (TDS), EC, and pH of water samples were measured
the Proterozoic Shillong Group lacks primary porosity. in the field immediately after the sampling. Ca and Mg
Groundwater circulation and occurrence are influenced were determined by standard Ethylene Diamine Tetra
by physiography, weathering zones, and linked zones of Acetic acid (ETDA). Na and K were measured by a
weakness or secondary porosity, such as joints and faults. Flame photometer, Cl by Volhard’s titration and HCO 3
Groundwater exists in two states: unconfined in weathered by acid-base titration, and SO4 by Systronic turbidity
residuum and semi-confined in secondary porosity such meter. SiO2 was measured by a UV spectrophotometer.
as cracks and fissures. The depth to water level ranges Trace elements Zn and Fe were measured by Atomic
from 2 m to 26 m below ground level. The majority of the Absorption Spectrophotometer (AAS) and U by UA3
area is occupied by quartzite and granite rocks having a Laser Fluorometer. The entire database has 14 variables,
groundwater potential of 5 m3/hr-15 m3/hr [20,21]. In most of including physicochemical parameters (TDS, conductivity,
the areas in valley sections, the topography cuts the water pH), cations (Na, K, Ca, Mg,), anions (Cl, CO3, HCO3,
table and forms a natural spring. SO 4 ), and trace elements (Fe, Zn, U) in Table 2.
Table 2. Hydrogeochemical data summary statistics

Arithmetic Standard WHO Limits ISI Limits 1974
Parameters Minimum Maximum Median
Mean Deviation 2011 [29] [52]
Na 0.05 12.10 2.25 2.75 2.48 200

K 0.05 5.60 0.65 0.92 1.01 10
Ca 0.05 16.00 2.20 3.74 3.63 100-200 75-200
Mg 0.10 13.00 1 1.25 1.62 50 30-100
Cl 3.00 36.00 6 7.52 5.14 250 600
HCO3 3.00 393.40 21.00 39.37 61.75 200
Fe 5.00 625.00 47.50 107.11 138.53 0.1 0.3
TDS 2.00 180.00 35 42 31.07
pH 3.40 8.40 6.90 6.79 0.67 6.5-8.5 6-9
COND. µS/cm 5.00 284.00 30.50 42.51 38.88 1.6 0.8-2.4
ALK. 5.00 644.80 35 64.78 100.99 600*
TH 0.50 71 9.40 13.60 11.59 500 300
SiO2 0.90 40.43 8.98 11.12 8.75
13
Table 2 continued
Arithmetic Standard WHO Limits ISI Limits 1974

Parameters Minimum Maximum Median
Mean Deviation 2011 [29] [52]
Zn ppb 0.50 9039 3.00 98.80 876.90 5 5

SO4 3 3 3 3 0 200-400 150-400
NMg 0.05 0.83 0.22 0.25 0.15
pE 12.38 17.38 13.88 13.98 0.67
Eh (V) 0.73 1.03 0.82 0.83 0.04
% Na 2.19 69.63 34.94 34.01 16.19
SAR 0.07 8.51 1.70 2.07 1.63
PS 0.09 1.02 0.20 0.23 0.15
PI 28.60 1493.33 89.41 130.09 163.06
MR 5.96 97.06 34.81 37.21 16.21
CR 0.02 16.90 0.55 0.76 1.63
CAI-I –3.53 0.81 –0.37 –0.57 0.77
KI 0.02 2.13 0.42 0.52 0.41
Note: 1. The number of samples n = 108, all units in mg/L, except those mentioned *Central Pollution Control Board India. 2.
Uranium except for three samples, all are below detection limits, 0.7 ppb UM/2, NONG/5, and 0.8 ppb MYL/4. Whereas all other
trace elements values are below detection limits for the entire investigated area.
The U content is <0.5 ppb in all the samples except three

samples which show 0.7 ppb (UM/2, NONG/5) and
3a
0.8 ppb (MYL/4), these sample locations are shown in
Figure 3a and 3b as red hollow diamonds. All other trace
elements analyzed are below detection limits for the entire
area investigated. Water chemistry data are frequently
hampered by censored values, in that the concentration of 3b
certain elements is reported only as less than (<) or greater

than (>). These values represent the lower and upper
detection limits of the instrument. These censored values
should be replaced with unqualified values since they are
3c
unsuitable for imaging and statistical analysis [24,25]. The
strategy followed for the present study for the replacement
of less-than values by 0.55 times the lower detection limit
and greater-than values by 1.7 times the upper detection
limit, given by [26]. This method is followed to fill the < the 3d
detection limit values in some uranium and SO4. Spatial
distribution images were generated using Golden Surfer
with standard gridding and interpolation methods such
as I2DW. SRTM digital elevation model was generated
using Global mapper. Landsat 8 OLI and Sentinel 2 data 3e
were interpreted for lithostructural mapping. Statistical

analysis is done on the XLSTAT plugin for excel. The
uranium along with the SO4 image not generated as well
as not considered for statistical analysis since it shows
3f
almost constant values for the entire area of investigation.
Geological, radiometric and hydrogeochemical multi- Figure 3. Images of Physicochemical parameters. 3a:
elemental litho- and pedo-geochemical investigations pH Image, 3b: Conductivity Image, 3c: Eh image, 3d: pE
were conducted for the investigated area. Fig.3: Images of Physicochemical
image, 3e:parameters 3a: pH 3f:
TDS image, Image, 3b Conductivity
Total HardnessImage image
3c: Eh image, 3d: pE image, 3e: TDS image, 3f: Total Hardness image
14
5. Results and Discussions with an average of 0.83V indicating the water has strong
oxidising environment Figure 3c, [27,30,31]. pE is calculated
5.1 Physicochemical Parameters pH, Electrical in the field by measuring pH (pe = 20.775-pH). pE is
Conductivity, Eh, pE and TDS
varying from 12.38 to 17.38 with an average of 13.88
pH is a term used universally to express the intensity of (Figure 3d). This is also unitless as the pH of water. The
the acid or alkaline condition of a solution. It is observed uranium content measured 0.7 ppb (n=2) to 0.8 ppb (n=1)
that the pH values of the water samples ranged from 3.4 at localities are shown as red triangles in Figure 3a and
to 8.4 with a mean value of 6.79 in the study area (Figure 3b rest of the samples measured below detection limits
3a). Acidic values observed may be due to the influx of of 0.5 ppb. The low U content in the water is caused by
rainwater of low alkalinity. The recommended values for the lesser residence time available for water in rocks due
irrigation water are from 6.5 to 8.4, and the permissible to the higher gradient of terrain and high rainfall. This
limits as per world health organization [27] are between 6.5 phenomenon is also reflected by low conductivity and low
to 8.5.
TDS 2-180 mg/L with an average of 42 mg/L (Figure 3e).
Electrical conductivity ranges from 5 to 284 µ mhos/
cm with an average of 42.51 µ mhos/cm (Figure 3b) the 5.1.1 Total Dissolved Solids
highest values are seen in the vicinity of SW of Mawlai
and Mawiong. According to world health organization [27] TDS varies from 2 mg/L to 180 mg/L with an average of
guidelines; the permissible limit of EC is 1400 µ mhos/cm 43 mg/L and falls under the freshwater category (Table 3).
(Table 3). The oxidation-reduction potential (Eh = 0.059 The highest values are seen around SE of Mawlai and NE
pE) varies in the investigated area from 0.73 V to 1.03 V of Umlingka villages (Figure 3e).
Table 3. Classification of stream water quality based on suitability of water for drinking and irrigation and supply purposes.
Parameter Range Class Number / %
<250 Excellent 107/99.1%
250-750 Good 1/0.9%
Conductivity 750-2000 Permissible Nil
2000-3000 Doubtful Nil
>3000 Unsuitable Nil
0 -500 Desirable for Drinking 108/100%
0 -1000 Freshwater Permissible for drinking 108/100%
Up to 3000 Permissible for Drinking Nil
TDS >3000 Unfit for drinking water Nil
1000-10000 Brackish Water Nil
10,000-100,000 Saline Water Nil
>100,000 Brine Nil
<20 Excellent 27/25%
20-40 Good 40/37.04%
Na% 40-60 Permissible 34/31.48%
60-80 Doubtful 7/6.48%
>80 Unsuitable Nil
<50 Suitable 88/81.48%
MR
>50 Unsuitable 20/18.52%
<75 Soft 108/100%
75-150 Moderate Nil
TH
150-300 Hard Nil
>300 Very hard Nil
15
Table 3 continued
Parameter Range Class Number / %

<20 Excellent 108/100%
20-40 Good Nil
SAR 40-60 Permissible Nil
60-80 Doubtful Nil
>80 Unsuitable Nil
<1 Suitable 90/83.33%
KI
>1 Unsuitable 17/15.74
<1 Galvanised Pipes to be used 89/82.41
CR
>1 Polyvinyl pipes to be used. 19/17.59%
5.1.2 Total Hardness (TH) and Mawkynroh respectively (Figure 4b).
The TH of water is calculated as under: 5.2.3 Calcium (Ca)

(1) In general, Ca shows low concentration all over the
Total hardness varies from 0.50 to 71 with an average study area. The values vary from 0.05 mg/L to 16 mg/L
of 13.6 in Table 3 and Figure 3f. Temporary hardness is with an average of 3.74 mg/L (Figure 4c). Few high
mainly due to calcium and magnesium ions and iron in concentrations of Ca are observed near Nongpinom,
the water that gets removed during heating. Permanent Nongumlong and Mawlai, and Mawiong areas across the
hardness is due to chlorides sulfates and nitrates of unconformity also from Barapani to Tyrsad formation.
Ca2+ and Mg2+ ions that get removed by ion-exchange
processes. The hardness of water limits its use for 5.2.4 Magnesium (Mg)
industrial purposes. For drinking water, the degree of
The dissolved Mg shows very good correlations with
hardness has been classified in terms of its equivalent
Ca in general, but in the present case, Mg values are very
concentration of CaCO3. Table 4 shows that all the water
low in the study area ranging from 0.1 mg/L to 13 mg/L
samples of the study area belong to the soft category.
with an average of 1.62 mg/L (Table 3). The high Mg
In some studies, a significant correlation was observed
values are observed around Mawiong and in between
between hardness and heart diseases, in contrast, several
Umlyngka and Nongumlong (Figure 4d).
epidemiological studies suggest that water hardness
protects against diseases [28]. 5.2.5 Chloride (Cl)
5.2 Major Ions In the present studied area, it varies from 3 mg/L to
36 mg/L with an average of 7.52 mg/L (Table 3). The
5.2.1 Sodium (Na)
spatial distribution is shown in (Figure 4e). The highest
The Na+ concentrations are varying from 0.05 mg/L to values are seen in between the Mawlai and Umlingka
12.1 mg/L with an average of 2.75 mg/L (Table 3), high areas (Figure 4e). The principal effects on the chloride
zone is seen near the southwest of Mawlai and northwest distribution are attributed to rainfall, lithology, and land-
of Umlygka village (Figure 4a). The major factors use patterns. Chloride in surface and groundwater is from
affecting Na distribution are similar to those of chloride both natural and anthropogenic sources, such as run-
and, to a lesser extent, SO42−. off containing road de-icing salts, inorganic fertilizers,
landfill leachates, septic tank effluents, animal feeds,
5.2.2 Potassium (K)
industrial effluents, irrigation drainage, and seawater
Generally, low potassium concentrations are observed in intrusion in the coastal area. In natural waters, chlorides
the entire survey area. The K values vary from 0.05 mg/L can be considered ubiquitous. Because chlorides are
to 5.6 mg/L with an average of 0.92 mg/L, high zone more of an aesthetic than a health concern (although
is seen near the southwest of Mawlai and northwest of high concentrations can be harmful to those with heart
Umlygka village. Other areas of high K are observed over or kidney ailments), Chloride concentration in drinking
the granitic areas of Kyrdem and Mylliem near Umsophoh water may be particularly important to persons on low salt
16
Table 4. Pearson’s correlation of various parameters
Na K Ca Mg Cl HCO3 Fe TDS pH COND. ALK. TH SiO2 Zn NMg
Na 1
K 0.76 1
Ca 0.67 0.62 1
Mg 0.15 0.01 0.62 1
Cl 0.64 0.67 0.49 0.02 1
HCO3 0.07 0.22 0.29 0.29 –0.11 1
Fe –0.02 0.18 –0.07 –0.07 –0.08 0.50 1
TDS 0.74 0.65 0.81 0.46 0.69 0.00 –0.16 1
pH –0.28 –0.10 0.31 0.38 0.14 0.18 –0.05 0.09 1
COND. 0.81 0.73 0.92 0.54 0.62 0.29 –0.03 0.93 0.09 1
ALK. 0.07 0.21 0.28 0.29 –0.12 1.00 0.50 –0.01 0.18 0.28 1
TH 0.37 0.21 0.73 0.73 0.04 0.48 0.12 0.32 0.33 0.56 0.48 1
SiO2 0.21 0.12 0.65 0.66 –0.19 0.39 –0.01 0.27 0.29 0.47 0.39 0.81 1
Zn –0.09 0.03 –0.12 –0.04 –0.04 0.46 0.50 0.04 –0.05 0.05 0.47 –0.09 –0.08 1
NMg –0.62 –0.42 –0.32 0.29 –0.33 0.22 0.08 –0.34 0.33 –0.35 0.23 –0.04 –0.04 0.22 1
NB: Bold positive correlations and red strong negative correlation
diets. The maximum contaminant level for public water Bicarbonate raises the pH of water, and high bicarbonate
supplies is 250 mg/L [29]. levels may be linked to a high pH.
5.2.6 Bicarbonate (HCO3) 5.2.7 Alkalinity

The levels of HCO3 in samples from the study area Alkalinity varies from 5 to 644.8 with an average of
are between 3 mg/L to 393.4 mg/L with an average of 64.78 (Table 3, Figure 4g). Low alkaline values were
39.37 mg/L. Results showed that only 1.8% of the observed due to the leaching of dissolved constituents
groundwater samples had higher levels of HCO 3 , into the water and the absence of calcareous rocks in the
exceeding the permissible limit. The high HCO3 levels area. The CaCO3 is not a health hazard [31,32]. Carbonate
are observed in Umsohpho and SW of Mowiang Areas alkalinity makes up the majority of total alkalinity in the
(Figure 4f). Bicarbonate concentration is a reliable natural environment. Alkalinity can also be influenced
measure of the extent of acid neutralization that has taken by other natural elements. The dissolved carbon dioxide
place in natural waters [30]. Bicarbonate anions are often species, bicarbonate, and carbonate, provide alkalinity in
dominant in natural stream waters and have a major practically all natural fluids. Borate, hydroxide, phosphate,
influence on the solubility of several cations with which silicate, nitrate, dissolved ammonia, conjugate bases of
they form stable complexes. The higher proportions of various organic acids, and sulfide are some of the most
bicarbonate with other anions indicate weathering of prominent noncarbonate sources of alkalinity. Alkalinity
primary silicate minerals dominated by alkaline earth [31]. is vital because it buffers pH fluctuations that naturally
Other anions such as chloride and sulfate may be present occur during photosynthetic cycles, water exchanges, and
in modest amounts in water with high bicarbonate levels. other processes.
17
as compared to mean river water). High Fe values are

seen in the area around Mawklot, Nongumlong, and
4a west and northwest of Mawlai and Mawiong mainly in
Tyrsad formations; north of Lummawsiang, and west of
Umsohphoh in Barapani formations (Figure 5a). Iron is
usually found in groundwater in the form of Fe2+, although
it can be presented as Fe3+, FeOH2+, or FeOH+, depending
on pH, oxygen content, and chemical interaction with
4b other elements [33]. At pH values of 4.5 to 9, soluble Fe
is usually in a ferrous state, especially if the medium
is reducing as in most groundwater. Fe oxidizes under
the action of air or by contact with chlorine, going into
the ferric state, and can thus be hydrolyzed to give an
insoluble iron hydroxide [34]. The Fe occurs as Fe (OH)2+,
4c Fe (OH)4−, and Fe(OH)3(aq) were also observed in smaller
proportions as expected, according to the pH values of
this study (3.4 to 8.4 with a mean value of 6.79 in Figure
3a). Fe(OH)4− species showed a more significant presence
in sites with pH around 8.4 and positive redox potential.
4d A criterion of 0.3 mg/L for iron is the recommended limit
for domestic water supplies, primarily because of the
taste threshold of iron in the water whereas for freshwater
aquatic life the limit prescribed is 1 mg/L [29,35].
5.3.2 Silica Image (SiO2)

4e
SiO2 varies from 3.42 mg/L to 40.43 mg/L with an
average of 11.12 mg/L (Figure 5b). Hydrogen percentage
plays an important role in rock weathering. The
dissolution rates of most silicate minerals are independent
of pH (Figure 3a) in the circumneutral region; they
4f increase with decreasing pH in the acid region and
increase with increasing pH in the alkaline region
(Figure 3g). The alkaline nature of groundwater favours
the dissolution of secondary minerals. A good spatial
correlation between pH and silica is observed in certain
4g areas around Mawiang-Mawlai, Nongumlong -Maklot,
and Lumawsiang.
5.3.3 Zinc
Figure 4. Cations, Anions Images. 4a: Sodium Image, 4b:
Potassium Image, 4c: Calcium Image, 4d: Magnesium Zn 0.5 ppb to 9039 ppb with an average of 98.8 ppb
Image, 4e: HCO3 Image, 4f: Cl Image, 4g: Alkalinity Image. (Table 3). Zinc is naturally present in water. The typical
zinc content in saltwater is between 0.6 and 5 parts per
billion. Zinc concentrations in rivers are usually between
5.3 Trace Elements
5 and 10 parts per billion. Very high Zn content in water is
5.3.1 Iron (Fe) found in the area around Umsohphoh where the Zn values
rise to 9039 ppb (Figure 5c). The high concentration is
In the present study, Fe varies from 5 mg/L to 625 mg/L also observed in the area around Shillong ranging from
with an average of 107.11 mg/L (Table 3), and its spa- 19 ppb-3356 ppb with an average of 552 ppb along with
tial distribution is shown in Figure 5a. The surveyed high Fe, and Mn values [21]. This zinc anomaly is on
area shows marked enrichment of Fe (178.20 times Barapani formation in the vicinity of Kyrdem granite and
18
is associated with lineaments. The area between Shillong HCO3 > Cl > SO4. The major cations and anions are plotted
city and Umsohphoh warrants detailed geophysical on Piper’s trilinear diagram (Figure 6a) [37].
investigation for Pb-Zn mineralization. The trends from the CaHCO3 water to the NaHCO3
Zinc can, however, be toxic to some species of fish water indicate an evolution of the water and cation
at much lower concentrations than the standard limit for exchange of Ca for Na. Dominated by Ca2+ and HCO3-
drinking water [36]. Sensitive species may be killed by derived from the weathering of minerals in the bedrock,
concentrations of a few hundred micrograms per liter. including calcite the most easily weathered mineral in the
Zinc solubility is affected by the temperature and pH aquifer. Low concentrations of Na+ in the CaHCO3 waters
of the water. Zinc is insoluble in water when the pH is
indicate little cation exchange and dissolution of Na-
close to neutral. With rising acidity, solubility rises. For
minerals. The CaHCO3 waters represent recharge waters
domestic water supplies, the concentration of zinc should
with short residence times. The NaHCO3 water type is
be below 5.0 mg/L to protect against undesirable aesthetic
the most evolved of the waters and derives its Na+ from
effects [29,35]. Zinc has a nutritional value as a trace element
cation exchange of Ca for Na and K as well as dissolution
and is found in the human body in amounts of about 2.3
mg. Its primary roles include enzymatic reactions and of plagioclase which also results in high SiO 2 [37] .
DNA replication. Zinc is found in the human hormone NaHCO 3-dominated (103 samples) because of cation
insulin, and it plays a vital role in sexual development. exchange and plagioclase, SiO2 dissolution. Predominant
A daily dose of 2 mg-3 mg is recommended to avoid silicate weathering and limited carbonate dissolution are
deficiency. Because the human body only absorbs 20- also indicated by the Ca/Na Vs HCO3/Na plot and Ca/
40% of the zinc included in the diet, many individuals Na Vs Mg/Na plots (Figure 6c, 6d). HCO3Ca-Mg type
drink zinc-rich mineral water. Tastelessness and a loss water (only 5 samples) indicates major components
of appetite are two symptoms of zinc deficiency. The of surface recharge and water-rock interaction in
immunological and enzyme systems of children may groundwater only limited since the area has high relief
be harmed. hence the water has less time to interact with country
rocks. Hydrogeochemical facies mapping [38] shows that
six samples belong to Ca-Mg facies, one sample to Cl-
SO4 facies, five samples to bicarbonate, fourteen samples
show Ca-Na facies, six samples to Cl+SO4+HCO3 facies,
six samples to Cl+SO4+HCO3 ten samples to Na-Ca, and
66 samples belong to HCO3+Cl+SO4 facies (Figure 6b).
Figure 5. Trace elements Images. 5a: Iron Image, 5b: 6a: Piper trilinear diagram for hydrogeochemical facies for
SiO2 Image, 5c: Zinc Image
the groundwater samples of Shillong basin [37]. A Calcium
Type, B Sodium Potassium Type, C Magnesian Type, D
6. Hydrogeochemical Facies Bicarbonate, E Chloride Type, F Sulphate Type, Type;
The water is dominated by Ca, followed by Na > Mg > K, G-Sec. Alk. (Carbonate Hardness), H-Sec. Salinity (Non
except in a few samples where Mg dominates (n=5samples) carbonate Hardness), I-Primary Salinity (Noncarbonate
the cations. In anionic chemistry, the order of abundance is Alk.), J-Pri. Alk. (Carbonate Alk.), N-Neutral Type
19
6.1 Indices of Base Exchange

Changes in the chemical composition of groundwater
along its flow path can be understood by studying the
Chloro-Alkaline Indices (CAI). Schoeller [40,41] suggested
2 Chloro-Alkaline Indices (CAI) 1, 2 for the interpretation
of ion exchange between groundwater and the host
environment. The Chloro-Alkaline Indices I are calculated
from the following relations:
(2)
The choloroalkaline indices (CAI) can be either positive
6b: Piper diagram for the facies mapping approach for or negative depending on whether the exchange of Na
stream water samples from Shillong Basin after [39]. A and K is from water with Mg and Ca in rock/soil or vice
Calcium Type, B Sodium Potassium Type, C Magnesian versa. If Na and K are exchanged in water with Mg and
Type, D Bicarbonate, E Chloride Type, F Sulphate Ca, the value of the ratio will be positive, indicating a base
Type, Type; G-Sec. Alk. N-Neutral Type, 1 Calcium- exchange phenomenon. The negative values of the ratio
Magnesium, 2 Chloride-Sulphate, 3 Sodium-Potassium, will indicate chloroalkaline disequilibrium and the reaction
4 Bicarbonate, 5 Bicarbonate-Chloride-Sulphate, 6 as a cation-anion exchange reaction [41]. In the present
Calcium-Sodium, 7 Chloride-Sulphate-Bicarbonate, 8 case, 89% values (96 No.) are negative ranging from
Sodium-Calcium 0.00 to -3.525 (Cation-anions exchange), and 11% values
(12 No.) are positive ranging from up to 0 to +0.808 i.e.,
showing a slight base exchange phenomenon in the area
6c around Nongpinom and Umlyngka (Table 3). The result
Carbonate
Dissolution suggests that cation exchangeable is primarily the main
mechanism responsible for the chemical composition of the
groundwaters in the studied area (Figure 7c).
6.2 Normalized Mg
In particular, the magnesium enrichment associated
with intense and pervasive chlorite alteration that
accompanies the four known deposits is reflected
Ca/Na wt% in the major element composition of groundwaters
from the vicinity of each known deposit. Mg 2+ is very
6c: Ca/Na vs HCO3/Na much more than Ca 2+ and Na + + K + in the areas of
magnesium metasomatic alteration. NMg can be used as
a hydrogeochemical exploration indicator for uranium
deposits. This can be determined by Normalised Mg2+ and
6c
Carbonate is expressed as NMg as follows:
Dissolution
(3)
All values in meq/L [42]. The NMg varies from 0.048 to

0.83 with an average of 0.23 (Figure 7b). In general, NMg
values are <0.8 indicating that they are collected from
non-Mg metasomatic areas i.e., nonmineralized aquifers.
Ca/Na wt%
However, one sample collected from the Mawklot
area (MKT-1)
Fig.6: Plots showing predominace shows
of silicate a 0.83and
weathering NMg value
minor showing Mg
carbonate
6d: Ca/Na vs Mg/Na dissolution. 6c:Ca/Na
metasomatism. /Na, 6d
vs HCO3This Ca/Na
zone vs Mg/Na
coincides with high Ra(eU3O8) =
Figure 6. Plots showing predominace of silicate 2 to 4 ppm, Ra(eU3O8)/K = 2-7 × 10-4 & ThO2/K = 10-15 ×
weathering and minor carbonate dissolution. 10 -4. NMg shows weak positive correlations with Mg
20
7a
7b
7c
7d
7e
7f
7g
7h
Figure 7. Calculated Water Quality Images. 7a: Chloroalkalinity Image, 7b: NMg, 7c: MR, 7d: %Na, 7e: SAR, 7f:
Fig. 7: Calculated Water Quality Images. 7a: Chloroalkalinity Image, 7b: NMg, 7c:MR, 7d:%Na, 7e:SAR,
Kelly’s Index, 7g: Permeability Index, 7h: Corrosive ratio Image.
7f: Kelly’s Index, 7g: Permeability Index, 7h: Corrosive ratio Image.
21
(0.29), HCO3 (0.22), pH (0.33), Alk (0.23) and Zn 90.22). 6.4 Sodium Percentage
NMg shows strong negative correlations with Na (–0.62)
and weak negative correlations with K (–0.42), Ca (–0.32), Sodium is an essential ion for irrigation water classifi-
Cl (–0.33), TDS (–0.34), and cond. (–0.35) in Table 4. cation because it inhibits permeability, given its reactivity
The radiometric surveys in the area resulted in locating with soil. The %Na is computed as:
two low-intensity uranium anomalies (Figure 1). Medium (5)
to high order radioactivity was recorded in ironstone over
where all ionic concentrations are expressed in meq/L.
an extension of 100 m × 50 m around 1.5 km northwest
According to Wilcox [43], in all-natural waters, %Na+ is a
of Nongkseh (Lat: –25°34’56.6”, Long: –91°51’28.1”),
common parameter to assess its suitability for irrigation
The rock samples analyzed 0.022% to 0.046% eU3O8, <
purposes as shown in Table 2. Na+ ions are absorbed by
0.010% to 0.017% U3O8, 0.040% to 0.089% ThO2 and <
clay particles when the concentration of Na+ in irrigation
0.005% to 0.005% Ra(eU3O8). It occurs as floats on the
water is high, displacing Mg 2+ and Ca 2+ ions. This
surface of the soil which is a natural phenomenon. This
exchange of Na+ in water for Ca2+ and Mg2+ in soil lowers
radioactive anomaly is nearer to the unconformity and
the permeability of the soil and eventually leads to poor
nonradioactive away from the unconformity. The data
internal drainage, resulting in hard soils when dry [44,45].
indicates the mixed nature of the anomaly. The high
The values of %Na+ of the study area vary from 2.19%
content of ThO 2 is due to the presence of radioactive
to 69.63% with an average value of 34.94% (Table 2,
heavy mineral resistates like monazite and sphene in
Figure 7d) which falls in the excellent (27 samples 25%)
the rock. Another low order radioactivity was recorded
to good category (40 samples 37.04%), showing that the
in graphite schist over 10 m × 2 m around 1 km NNE
groundwater of the study area is suitable for drinking as
of Nongumlong on the way to Umiam river analyzing
well as irrigation; meanwhile, 34 samples (31.48%) are
25 ppm eU3O8, 16 ppm ThO2, 10 ppm Ra (eU3O8) (Lat:
permissible and 7samples (6.48%) are doubtful while
– 25°34’15”, Long: – 91°50’08” Figure 1). After 10
none samples are unsuitable category (Table 3). The EC
m away along with the same road section low order
ranges between 5.0 μS/cm and 284.0 μS/cm, in which the
radioactivity was also recorded in chloritic phyllite over
groundwater is excellent to a good category in Figure 8;
an extension of 100 m × 2 m analyzing 14 ppm to 30 ppm
therefore, the groundwater can be useful for irrigation.
eU3O8, 11 ppm to 26 ppm ThO2, and 3 ppm to 8 ppm Ra
(eU3O8). Spatial association of low order anomalies and
Mg metasomatism warrants subsurface investigations for
uranium mineralization possibilities.
6.3 Magnesium Ratio (MR)

In most water bodies, calcium and magnesium are in
a condition of balance. More magnesium in the water
reduces crop output. Because the study area’s rocks are
primarily Arenites and Phyllites, with some basic and
conglomerate strata, the majority of the water has more
calcium than magnesium. The magnesium ratio was
determined using the following equation:
(4)
The MR values vary from 5.96 to 97.06 with an
average of 130.09 (Table 3). The high values are
Figure 8. Electrical conductivity vs. %Na plot after [43]
Fig.8: Electrical conductivity vs. %Na plot after [43]
observed in the area around Umsohphoh and along the
unconformity as small circular anomalies but it constitutes
6.5 Sodium Adsorption Ratio (SAR)
very small areas, while predominantly the study area has
lower MR values (Figure 7c). The 88 samples (81.48%) Sodium adsorption ratio (SAR) is a measure of the
show <50% values i.e., suitable for irrigation purposes alkali or sodium hazard to crops. When the sodium
while 20 samples (18.52%) show >50% values and is not concentration is high, sodium ions tend to become
suitable irrigation purposes (Table 3). adsorbed onto the clay soil particles, displacing Mg2+ and
22
7samples (6.48%) are doubtful while none samples are unsuitable category (Table 3). The EC
ranges between 5.0 μS/cm and 284.0 μS/cm, in which the groundwater is excellent to a good
category in Figure 8; therefore, the groundwater can be useful for irrigation.
见文件
Advances
Figurein
8. Geological and Geotechnical
Electrical conductivity vs. %Na Engineering
plot after [43] Research | Volume 04 | Issue 02 | April 2022
6.52+Sodium
Ca Adsorption
ions. Exchange of NaRatio+
for(SAR)
Ca2+ and Mg2+ results in signifies its deficit in waters [48]. A Kelly’s ratio of more
Sodium adsorption ratio (SAR) is a measure of the alkali or sodium hazard to crops.
soil
Whenwith poor internal
the sodium drainage
concentration is high,and restricted
sodium circulation
ions tend than one
to become adsorbed onto indicates
the clay soilexcessive sodium in water. Therefore,
of air and
particles, water when
displacing Mg2+ and wet. Ca2+Such
ions.soils usually
Exchange of Naform
+
hard
for Ca 2+
and Mg
waterresults
2+
within Kelly’s
soil with index less than one is suitable for
poor internal drainage and restricted circulation of air and water [43,44]when wet. Such soils usually
and unmanageable clods when dry, SAR is defined as :
form hard and unmanageable clods when dry, SAR is defined as [43,44]: irrigation, while those with a ratio of more than one is
 =

-------------------(7) 6.6 Kelly’s
unsuitable Index The KI varies from 0.016 to 2.13
(12.96%).
( + )/ (6)
where all ionic concentrations are expressed in meq/L. The SAR of the study area ranges with an Kelly’s
average Index
value(KI) is used
of 0.52 for the
(Table 2). classification
In the presentof water for irr
where0.066
between all ionic concentrations
and 8.514, with an average are value
expressed in (Table
of 2.074 meq/L.2, Table calculated
5; Figure by
7e) the following
which formula; where ions are expressed in meq/L
study, 12.96% of the water samples are unsuitable for
The SAR
indicates thatofnothe studyhazard
alkalinity area isranges between
anticipated 0.066
in the study areaand
and theKIEC=  +
ranges between 5.0
---------------------------(8)
and 284.0 μS/cm, irrigation  2+with more
2+
9. than one KI is in the NW of Mawlai
8.514, with an in which the
average groundwater
value of 2.074 classifies
(Tableas2,excellent
Table to 5; a good category in
+ Figure
Most of the samples fall into the C1S1 category (Low salinity and low and SWKI of Mawtawar
sodium) (>1) showsvillages
of waters an excess (Figure 7f). While
of sodium and87.04%
KI (<1) signifies it
Figure
requiring7e) goodwhich indicates
drainage [46]
. Cropsthatwith
no alkalinity hazard is
good salt tolerance shouldKelly’s
be selected; gypsum
are ratiofor
suitable of irrigation
more than one shows
which indicates
KI<1 excessive
(Table sodium in wat
4,
anticipated
amendments make in theit study
possible area andthis
to use thewater
EC ranges
while onlybetween
two samples are in the C2S1 field
(Figure 9). Therefore (medium salinity and lowthe sodium), Kelly’s
Figure hazard
based on the sodium index
7f). class theless than one is suitable for irrigation, while those with a
5.0 μS/cm and 284.0 μS/cm, in which groundwater unsuitable
groundwater of the study area is suitable for irrigation. SAR values greater than 6(12.96%).
to 9, the The KI varies from 0.016 to 2.13 with an averag
classifies as excellent
could be to a goodtocategory in Figure 9.problemMost on In the present study, 12.96%
irrigation water expected cause a permeability shrinking
6.7 and swelling
Permeability Index (PI)of the water samples are unsuitable for
of
typestheofsamples
clayey soils fallwhich
intoare theobserved
C1S1 category
in the north (Low salinity
of Mawlai and SWoneof Mawtawar
KI is in villages
the NW of Mawlai and SW of Mawtawar villages (Figu
(Figure 7e).
and low sodium) of waters requiring good drainage suitable The salt,for irrigation
calcium, which shows KI<1
magnesium, and(Table 4, Figure 7f).
bicarbonate
[46]
. Crops with good salt tolerance should 见文件 be selected; 6.7 Permeability
concentrations in soil Index
impact soil(PI)permeability, which also
gypsum amendments Figure 9. Diagrammakefor it USSL
possible to use this
classification water water
of irrigation Thequality
after [48]
affects the salt, ofcalcium,
irrigationmagnesium,
water over time.and Doneen
bicarbonate
[49] concentrat
while only two samples are in the C2S1 field (Figure 9). has permeability, which also affects the quality
evolved a criterion for assessing the suitability of water of irrigation water over tim
a criterion for
Therefore (medium salinity and low sodium), based on the for irrigation based on PI, calculated by using the formula: assessing the suitability of water for irrigation based on
sodium hazard class the groundwater of the study area is formula:
 ++ + 3−
suitable for irrigation. SAR values greater than 6 to 9, the  =  +++ +++ + × 100------------(9 (8) )
irrigation water could be expected to cause a permeability where all the ions are expressed in meq/L. PI ranges from 28.59 to
where all the ions are expressed in meq/L. PI ranges
problem on shrinking and swelling types of clayey soils 130.09 (Table 2). According to PI values, the groundwater 3 samples
from
in Class 28.59 II,toand 1493.33
the restwith73averages
samplesof(67.6%)
130.09 plot
(Tablein 2).
Class III. Class
which are observed
Fig.8: in the north
Electrical conductivity vs. %Naofplot
Mawlai
after [43] and SW of
Mawtawar villages (Figure 7e). According to PI values, the groundwater
categorized as good for irrigation with 75% or more 3 samples fall in of maximum
class I, 32 samples in Class II, and the rest 73 samples
Figure 7g). Class III waters are unsuitable with 25% of maximum pe (67.6%)
values
plot are seen
in Class III. near
Classthe Umsohpho
I and area which
Class II waters coincides with the Zn a
are categorized
5c.good for irrigation with 75% or more of maximum
as
permeability (Figure 10; Figure 7g). Class III waters are
见文件
unsuitable with 25% of maximum permeability [49]. Very high
Figure 10. PI vs TDS plot for water samples afte
values are seen near the Umsohpho area which coincides
with the Zn anomalyRatio
6.8 Corrosivity area also(CR)
in Figure 5c.
The corrosivity ratio is defined by the following formula after [5
− −4
+2
35.5 96
 − + 
_ ------------------(10)
3 3
2
100
where all the ions are expressed in ppm (Table 3). The vales vary in
mg/L to 16.90 mg/L with an average of 0.76 mg/L (Figure 7h). The CR
groundwater to induce corrosion of pipes and is expressed as the ratio
salts in groundwater. Corrosion can result in the loss of hydraulic cap
EC µ S/cm
SW of Umlingka, N of Mawlai, and SE of Lummawsiang where th
Fig.Figure 9. for
9: Diagram Diagram for USSL
USSL classification classification
of irrigation of[48].
water after irrigation chloride (PVC) pipes should be used (Table 3, Figure7h). Most of th
water after [48] shows CR <1 (Figure 7h) where galvanized pipes can be used.
7. Statistical Analysis and Unsupervised Classifica
6.6 Kelly’s Index Correlation matrix of all the hydrogeochemical data (Table 4)
of conductivity with TDS (0.93) Ca (0.92), Na (0.81), K (0.73), Cl (0.
6.6Kelly’s
Kelly’sIndex (KI) is
Index used for the classification of
[47]
Fig. 10: PI vs TDS plot for water samples after [49]
Figure 10. PI vs TDS plot for water [47] samples after [49]
water forKelly’s
irrigation purposes . KI is calculated by the
Index (KI) is used for the classification of water for irrigation purposes . KI is
following
calculatedformula;
by the where ions are
following expressed
formula; in meq/L.
where ions are expressed in meq/L.
 +
6.8 Corrosivity Ratio (CR) 11a
KI =
 2+ +  2+ ---------------------------(8)
(7)
The corrosivity ratio is defined by the following formu-
KI shows
KI (>1) (>1) shows an excess
an excess of sodium
of sodium and KI and
(<1)KI la(<1)
aftersignifies
[50]
: its deficit in waters [48]. A
Kelly’s ratio of more than one indicates excessive sodium in water. Therefore, water with
Kelly’s index less than one is suitable for irrigation, while those with a ratio of more than one is
unsuitable (12.96%). The KI varies from 0.016 to 2.13 with an average value of 0.52 (Table 2). 23
In the present study, 12.96% of the water samples are unsuitable for irrigation with more than
one KI is in the NW of Mawlai and SW of Mawtawar villages (Figure 7f). While 87.04% are
见文件
Figure 10. PI vs TDS plot for water samples after [49]
6.8 Corrosivity Ratio (CR)
The corrosivity ratio is defined by the following formula after [50]:
− −
35.5
+2 4
96
conductivity with PS and CR (Figure 11a, 11b) and Group
 − _
3 + 3
------------------(10)
(10) III consists of TH Mg and Ca with two independent
2
100
variables as Fe, pH, (Figure 11a, b). Group-II in Figure 11b
where all the ions are expressed in ppm (Table 3). The vales vary in the study area from 0.02
where all the ions are expressed in ppm (Table 3). The consists of a very low linkage of KR and SAR with %Na.
mg/L to 16.90 mg/L with an average of 0.76 mg/L (Figure 7h). The CR denotes the potential for
vales vary in to
groundwater theinduce
study corrosion
area from of 0.02 mg/L
pipes andtois16.90 mg/Las the
expressed Group-III consistsearth
ratio of alkaline of MR, and PI with CAI-I at some
to saline
with an average of 0.76 mg/L (Figure 7h). The CR denotes
salts in groundwater. Corrosion can result in the loss of hydraulic distance.
capacityThe of spatial
pipes. Indistribution
the area of these groups, in
the
SWpotential for groundwater
of Umlingka, N of Mawlai, to induce
and SEcorrosion of pipes where
of Lummawsiang the isCR
general, as value
under:>1, polyvinyl
chloride
and (PVC) pipes
is expressed as theshould
ratio ofbealkaline
used (Table
earth 3,
to Figure7h).
saline salts Most of
1) the South
area under investigation
of Mawlai all the three groups of waters
shows CR <1 (Figure 7h) where galvanized pipes can be used.
in groundwater. Corrosion can result in the loss of hydraulic are found granites and its vicinity area, TH moderate
7. Statistical
capacity of pipes. InAnalysis
the area SW and Unsupervised
of Umlingka, N of Mawlai,Classification
to high. Low conductivity. In the case of water quality
Correlation matrix of all the hydrogeochemical data (Table 4) shows positive correlation
and SE of Lummawsiang where the CR value >1, polyvinyl parameters also the same pattern is seen (Figure 11e).
of conductivity with TDS (0.93) Ca (0.92), Na (0.81), K (0.73), Cl (0.62), Mg (0.54), TH (0.56)
chloride (PVC) pipes should be used (Table 3, Figure 7h). 2) From Mawlai to Lummawsiang Group I and III
Most of the area under investigation shows CR <1 (Figure are found mixed TDS moderate to high. TH Moderate
7h) where galvanized pipes can be used. to high. Moderate to high conductivity. This zone has all
three groups but in Group II only six samples fall along
7. Statistical Analysis and Unsupervised Clas- with the group I and III.
sification 3) Further northwards from north of Lummawsiang
to the extreme northern end of the investigated area only
Correlation matrix of all the hydrogeochemical data
group III water is found. In general, these areas have low
(Table 4) shows positive correlation of conductivity with
TDS, TH low, and low conductivity. All the samples that
TDS (0.93) Ca (0.92), Na (0.81), K (0.73), Cl (0.62),
fall in this area are of group III only.
Mg (0.54), TH (0.56) and SiO 2 (0.47). TDS indicated
Various groups of water samples are also depicted in
high positive correlations with Ca (0.73), Mg (0.73), and
Figure 6a and 6b in the piper’s diagram.
conductivity (0.56) and moderate positive correlations
with HCO 3 (0.48) and Alkalinity (0.48). pH indicated 7.2 Factor Analysis
negative correlations with all the parameters. Na indicated
positive correlations with K (0.76), Ca (0.67), Cl (0.64), Factor analysis is one of the most important statistical
TDS (0.74), Conductivity (0.81) and negative with NMg tools for interpreting ground-water hydrogeochemistry. pH,
(-0.62). Ca has positive correlations with K (0.62), Mg EC, TDS, TH, Alkalinity, Na, K, Ca, Mg, Cl, HCO3, SiO2, Fe,
(0.62), TDS (0.65), Conductivity (0.73), SiO 2 (0.65) and Zn were the variables included in factor analysis. All the
and TH (0.73). Uranium and SO4 contents are constant factors showing >1.0 eigenvalues are considered significant
for the entire area of the investigation except for three based on the scree test. Factors were analyzed based on
values so not considered for statistical analysis. The strong, moderate, and weak loadings according to the total
values of >0.75, 0.75 to 0.5, and 0.5 - 0.3. These categories
hydrogeochemical data was standardized (X-µ/σ) for
are used to characterize the significance of factors. The first
unsupervised classification which forms a part of Machine
factor explains 33.75% variability and second is 16.44% and
learning for data mining.
the third is 10.7%, cumulative the three factors account for
7.1 Cluster Analysis 68.88% variability. The first factor shows strong loadings for
Cond, TDS, Na, and Ca, moderate positive loadings for TH,
The physicochemical parameters, anions, cations, and K, and Cl, and weak positive loadings for alkalinity, HCO3,
trace elements similarity between objects was measured SiO2, Mg, and Fe, almost all are showing positive loading
by squared Euclidean distances, and Ward’s method of of varying amounts thus it can be accounted for TDS and
divisive agglomerative hierarchical clustering (AHC) conductivity (Figure 12a). The second factor shows weak
method was used for cluster analysis [51]. The dendrogram positive loadings for Na, K Cl, TDS, and conductivity; strong
prepared based on the cluster analysis shows three distinct negative loadings for HCO3, Alkalinity and weak negative
classes /groups. Group-I consists of Na, K, Cl, TDS, and loading for Zn, and. The third factor shows weak positive
conductivity. It contains TDS and conductivity along with loading for Zn, Alkalinity, and HCO 3 whereas, strong
three independent variables Na, K, and Cl, indicating that negative loading for TH and weak to moderate negative
the TDS has contributions due to Conductivity, Na, K, loadings for pH, Mg, and Ca (Table 5) thereby indicating Zn
and Cl. Group II consists of HCO3 and Alkalinity. HCO3 variation along with alkalinity and bicarbonate variation in
and Alkalinity are closely related to other independent water (Figure 12b). The factor oblimin rotation shows that
variables Zn and SiO 2 and Group I consist of TDS the first D1 axis shows positive loading for all the ions with
24

11a
11a
11b
11b
25
11e
11e
Fig.11: Dendrogram of hydrogeochemical parameters using ward’s method. 11a: Dendrogram based on
columns and; 11b: Dendrogram based on rows; 11c based on columns (Water Quality parameters), 11d:
Figure 11. Dendrogram
basedof
onhydrogeochemical parameters
rows, 11e: Cluster groups of using
water overlayed ward’s
on TDS method.
clearly showing 11a: dispositions.
based on columns
the spatial Dendrogram
and; 11b: Dendrogram based on rows; 11c based on columns (Water Quality parameters), 11d: based on rows, 11e:
Cluster groups of water overlayed on TDS clearly showing the spatial dispositions.
12a
Figure 12. 12a: loading biplot of loading

Fig. 12a: F1 vsbiplot
F2 explains 50.19%;
of F1 vs F2 explains 12b:12b:
50.19%; F1F1vs
vs F3 biplot
F3 biplot explains
explains 44.45%.44.45%. 12c: Factor loading
after
Fig.12c:oblimin rotation
Factor loading D1 vs
after oblimin D2 biplot;
rotation D1 vs D2 12d: D1D1
biplot;12d: vsvsD3 biplot
D3 biplot
26
exception of Zn, Alkalinity, and HCO3. D2 axis shows +ve 8. Conclusions

loadings for Zn Alkalinity and HCO3 (Figure 12c). D3 axis
shows high loading for TH, Ca, Mg and weak loading for pH The hydrogeochemical evaluation of the area suggests
thereby indicating TH variation (Table 6, Figure 12d). that the pH is acidic to alkaline. All ionic concentrations
fall below acceptable WHO and ISI limits (except iron)
Table 5. Factor analysis of hydrogeochemical parameters and are found suitable for drinking. The area around
of the study area. Mawklot, Nongumlong, and west and northwest of
Final Mawlai and Mawiong, largely in Tyrsad formations;
Factor pattern F1 F2 F3 F4
communality north of Lummawsiang and west of Umsohphoh, mainly
Na 0.735 0.310 0.203 0.122 0.693 in Barapani formations, has high Fe content in water,
K 0.662 0.231 0.294 0.012 0.578 which needs to be treated to make it drinkable. Water is
Ca 0.790 0.027 –0.327 0.125 0.747 CaHCO 3, NaHCO 3, and CaMgHCO 3. CaHCO 3 waters
Mg 0.462 –0.112 –0.509 –0.015 0.485 represent recharge waters with short residence times
Cl 0.547 0.508 0.131 –0.284 0.655 due to high relief of the draining area, NaHCO3 water
HCO3 0.536 –0.798 0.275 0.016 1.000
indicates an evolution of the water and cation exchange
of Ca for Na due to plagioclase feldspar and silica
Fe 0.353 –0.158 –0.089 –0.496 0.403
dissolutions. Secondary mineral dissolution is observed
TDS 0.787 0.420 0.069 0.046 0.803
in areas around Mawioang-Mawlai, Nongumlong-
pH 0.187 –0.285 –0.341 0.146 0.254
Maklot, and Lumawsiang. CaMgHCO3 is characteristic
Cond. 0.821 0.298 0.273 0.035 0.840
of freshly recharged groundwater from precipitation.
Alk. 0.533 –0.798 0.281 0.013 1.000 The groundwater indices of Sodium Percent (%Na),
TH 0.671 –0.167 –0.717 –0.085 1.000 Kelley’s Index (KI), Sodium Adsorption Ratio (SAR),
SiO2 0.326 –0.216 0.144 0.422 0.352 Magnesian Ratio (MR), Electrical Conductivity (EC),
Zn 0.138 –0.396 0.287 –0.335 0.371 Total Dissolved Solids (TDS), USSL, and Wilcox index
Eigenvalue 4.725 2.301 1.497 0.681 were evaluated and found to be suitable for agro-industrial
Variability (%) 33.750 16.436 10.695 4.867
uses. Normalized Mg (NMg) shows areas of magnesium
metasomatic alteration zones around the Mawklot area.
Cumulative % 33.750 50.187 60.882 65.749
Permeability Index (PI) is found to be suitable in most
Values in bold correspond for each variable to the factor for areas and Corrosivity Ratio (CR) shows galvanized pipes
which the squared cosine is the largest to be used for water supply.
Unsupervised classification clearly shows three groups
Table 6. Factor pattern after Oblimin rotation of cations, anions trace elements, and physicochemical
parameters. AHC analysis also shows three groups having
D1 D2 D3
similar properties that are Group I consists of Na, K, Cl,
Na 0.804 0.070 0.022
TDS and conductivity, PS, and CR. Group II consists of
K 0.737 0.166 –0.075
HCO3 and Alkalinity, HCO3 and Alkalinity are closely
Ca 0.449 0.014 0.618 related to other independent variables Zn and SiO2, with
Mg 0.054 –0.070 0.695 the very low linkage of KR and SAR with %Na. Group III
Cl 0.768 –0.187 –0.030 consists of TH Mg and Ca with two independent variables
HCO3 –0.023 0.961 0.137 as Fe, pH, and MR, PI with CAI-I at some distance.
Fe 0.114 0.178 0.261 The factor analysis also indicated three major groups of
TDS 0.858 –0.083 0.145 the hydrogeochemical parameters. Thus, clearly defining
pH –0.186 0.091 0.467 the dimensionality of water types and their spatial
Cond 0.885 0.143 –0.008
distribution. All the three groups type of waters found the
lithological preferences i.e., Barapani Arenite, Barapani
Alk –0.022 0.963 0.131
Arenites contact with Mylliem granite, Tyrsad Argilllites,
TH 0.085 –0.084 0.989
and intervening Graphitic schists along the unconformity
SiO2 0.150 0.351 0.042
contacts in the southern part has all the three groups
Zn –0.042 0.527 –0.126
of waters. Followed by marginal exposures of Tyrsad
Values in bold correspond for each variable to the factor for Argillites, unconformity contact, and Barapani Arenites
which the squared cosine is the largest middle zone where the group II and III diminishes while at
27
the northernmost part with Barapani Arenite and Krydem Metals and Fuels. pp. 295-297.
granite contact zone has only group III type of waters. The [10] Bhattacharjee, C., Rahman, S., 1985. Structure and
area is devoid of uranium anomalies, except for the two lithostratigraphy of the Shillong Group of rocks of East
low-order radioactive anomalies near NW of Nongkseh, Khasi Hills of Meghalaya. Bulletin of Geological Min-
and the spatial association of the Mg metasomatic ing and Metallurgical Society India. 53, 90-99.
alteration zone warrants subsurface exploration. [11] Acharyya, S.K., Mitra, N.D., Nandy, D.R., 1986. Re-
gional geology and tectonic setting of Northeast In-
Acknowledgments dia and adjoining region. Memoirs of the Geological
The author is thankful to Atomic Minerals Directorate Survey of India. 119, 6-12.
for Exploration and Research (AMD) Northeastern [12] Ghosh, S., Chakraborty, S., Bhalla, J.K., et al., 1991.
Region (NER) Shillong for providing logistics and Geochronology and geochemistry of granite plutons
Chemistry laboratory AMD NER analytical facilities for from East Khasi Hills, Meghalaya. Journal of the
water samples. Geological Society of India. 37, 331-342.
[13] Ghosh, S., Chakraborty, S., Paul, D.K., et al., 1994.
Conflicts of Interest New Rb-Sr isotopic ages and geochemistry of gran-
itoids from Meghalaya and their significance in
The author declares no conflicts of interest regarding middle-to-late Proterozoic crustal evolution Indian
the publication of this paper. Minerals. 48(1&2), 33-44. Geoscience. 11, 1-16.
[14] Biswas, S., Isabelle, C., Grujic, D., et al., 2007. Ex-
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30

ARTICLE
Understanding Contributions of Divalent Cations in Mineral Carbon-
ation Using Artificial Neural Network
Abidoye, L.K.1,2* Oladipo, H.B.1
1. Process Engineering Department, National University of Science and Technology, Oman
2. Chemical Engineering Department, Osun State University, Nigeria
Article history The roles played by divalent cations (calcium, magnesium and iron)
Received: 21 February 2022 of rock minerals in the efficiency of mineral carbonation have been
investigated. Statistical modeling with Artificial Neural Network (ANN)
Revised: 21 March 2022 having configuration ANN[17-4-1] shows that carbonation efficiency
Accepted: 15 April 2022 largely increases as the quantity of calcium content increases. Averagely,
Published Online: 12 May 2022 there is approximately 5% rise in the original efficiency for 10% increase
in the quantity of calcium. This changes to 3.4% and 1.6% increases in
Keywords: efficiency, relative to the original efficiency for 20% and 30% increases in
calcium content, respectively. Iron content of minerals offers clear positive
Carbonation correlation to the carbonation efficiency. From the global average, there is
ANN approximately 17% rise in the original efficiency for 10% increase in the
Calcium quantity of iron. This increases to 29% and 41% over the original efficiency
for 20% and 30% increases in iron content, respectively.. The influence of
Magnesium
magnesium was found to be mainly negatively correlated to carbonation
Iron efficiency, after exceeding an unknown threshold. The global average of the
efficiency changes with magnesium content results in original efficiency
rising by 2% at 10% quantity increase and then reduces by 3% and 9% for
20% and 30% increase in magnesium quantity, respectively, relative to the
original efficiency. Thus, iron compounds are found to be most potent of
the divalent cations in carbonation reaction while calcium and magnesium
content should maintain a threshold ratio with silica content for improved
efficiency.
1. Introduction abundant and simple to apply, considering the scale of

greenhouse gases in the atmosphere and the diversity of
The task of stemming the global warming effects on emission sources, globally. One such solution process
the planet requires the deployment of very effective and is mineral carbonation, which offers the advantage of
capable solutions. The ultimate solutions should be cheap, permanent storage to CO2, in addition to cheapness and
Abidoye, L.K.,
Process Engineering Department, National University of Science and Technology, Oman; Chemical Engineering Department, Osun
State University, Nigeria;
Email: luqman@imco.edu.om
31
ease of application. The world is blessed with plethora of trained networks (ANNs) were then assessed to arrive at
abundant mineral resources to perform the task of miner- the best-performing ANN configuration. This best-per-
al carbonation [1]. The abundance of basalt is one strong forming configuration was then used to predict and fore-
factor that will positively upgrade the performance of cast carbonation efficiency based on the influences of
mineral carbonation in the fight against climate change [2]. mineralogical and chemical constituents of rock materials
Mineral carbonation offers the benefits of permanent and as well as the experimental conditions.
safe storage [2] with opportunities for making use of ubiq-
2.1 ANN Configuration
uitous earthly minerals [3], either as whole materials or as
mine wastes [4]. In this work, different ANN configurations were trained
To understand and improve the carbonation potentials and evaluated to arrive at the best network for predicting
of mineral, the chemical contents of the minerals must be mineral carbonation from rock characteristics and process
analyzed to know the roles each component play in the re- conditions. The networks were configured with feedfor-
action. According to Huijgen and Sanna et al. [5,6], carbon- ward structure while back-propagation algorithm was
ation rate is controlled by the diffusion of Ca2+ through the employed for the purpose of training. The ANN structure
solid Si-rich layers in silicate minerals. Thus, the presence was in the form ANN[X-Y-Z] where ‘X’ is the number of
of calcium is significant to determine the performance of input variables; ‘Y’ is the number of neurons in the hid-
mineral carbonation. Mineralogical and chemical com- den layer and ‘Z’ is the number of variables in the output
position were of great importance for the mineral car- layer. Different ANN configurations were tested using the
bonation process [7]. Ramli et al. [7] indicates that divalent approaches followed by Hanspal and Abidoye et al. [9,10].
cations, pH and particle size are important parameters to Networks were created using single layer alone but with
consider in the carbonation yield. This points to the im- different number of neurons in each of the layers. The
portance of calcium (Ca2+), magnesium (Mg2+) and others number of neurons was progressively increased for dif-
present in the rock minerals. The same concept can also ferent configuration. The simulation platform was MAT-
be extended to iron (Fe2+), making the group of common LAB (MathWorks, 2016). To implement the simulation
divalent cations. Thus, the optimum conditions for the oc- procedure in MATLAB, program files were prepared with
currence of mineral carbonation are greatly dependent on lines of code to create, train, validate and test the network
the experimental conditions and material properties [8]. as well as to generate the goodness of fit parameters of
From the above, it is clear that the chemical constitu- the data points using correlation coefficients (R 2) and
ents of the rock minerals are major determinants of the mean square error (MSE). In the script, the ‘While loop’
carbonation efficiency. While many factors can be con- procedure was used. The criteria of > ‘0.99’ coefficient
sidered, this work focuses on the roles played by divalent (R2) was set for the loop with twenty rounds of training
cations (calcium, magnesium, iron) in the success of for each configuration. The network with each configura-
mineral carbonation process with the aid of computational tion was subjected to rounds of training until satisfactory
tool- Artificial Neural Network (ANN). performance was obtained. So, if after twenty rounds of
This work aims to demonstrate the feasibility of uti- training, the criteria were not satisfied, the training was
lizing ANN to understand the patterns and the conditions stopped and the training of the next configuration began.
of contribution of divalent cations (calcium, magnesium The program divides the dataset randomly into 60%, 20%
and iron) of rock minerals in the efficiency of mineral and 20% corresponding to the data for training, validation
carbonation. The study will be among the first set of pub- and testing, respectively. In the training process, epochs of
lications, in the open literature, to utilize the concept of 200 was used as the stopping criterion. Epoch is the maxi-
machine learning to predict and forecast the carbonation mum number of times all of the training sets are presented
efficiency of rock materials based on mineral contents. to the network. Thus, the training stops if the maximum
number of epochs is attained. The network trainings thus
2. Materials and Methods
stopped when the number of iteration exceeded the stated
The methods of this investigation involved sourcing of number of epoch or other criteria is satisfied. At the end of
reliable data from literature with which different config- the training, network object is generated with indication
urations of ANN were trained. The performances of the of the best validation performance. The result from the
32
training giving the best performance was then selected for mances of various ANN configurations that were trained
each configuration, for comparisons and selection. in this work.
Mean squared errors (MSE)
2.2 Data Sources and Processing MSE computes the average of the squares of the errors
The data for this work were obtained from the car- between the observed value (Sobs) and the estimated value (Scal).
bonation data contained in the works [1,7]. The work is an (1)
experimental investigation of fundamental factors influ- where, N = total number of data points predicted, Sobs
encing mineral carbonation, using detailed kinetics of the = observed value of relative permittivity, and S cal =
process [1]. In the work, overall, 17 variables were extract- calculated value of relative permittivity, .
ed with a total of 4428 data points, but the focus of this
study is to understand the roles of divalent cations (calci- 2.4 Coefficient of Correlation (R2)
um, magnesium and iron). The variables and the summary The mathematical representation of coefficient of
of their statistical variation are shown in Table 1. correlation is expressed in Equation (2).
∑ (Y − Y pred )
2
2.3 ANN Model Performance Criteria R2 = 1−

measured
2
 ∑Y  (2)
The criteria used to evaluate the performance of differ-
∑  Y measured −
measured
N


 
ent ANN model configurations listed and explained below. where, Ypred is the network prediction value, Ymeasured
Equations (1) and (2) are mathematical representations of is the experimental response value and N is the total num-
detailed statistical analyses used to evaluate the perfor- ber of reading in the data points.
Table 1. Descriptive statistics of the input and output variables used in the machine learning
Stirrer Particle
PCO2 Solid Time, T NaCl NaHCO3 Mg Si Fe Al Cr Ni Mn Ca Carbonation
Variables speed size pH
(bar) (%) t (hr) (oC) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%) Yield (%)
(RPM) (µm)
Minimum 300 1 0.1 0.50 80 0 0 12.5 1.32 14.05 5.41 0.09 0.67 0.27 0.08 0.11 7 0.58
Maximum 1500 38.6 0.3 27.01 200 2 2 75 27.44 34.97 62.95 2 0.8 0.5 1 15.24 12 79.38
Average 247 27.29 0.12 3.38 159.80 0.89 0.84 28.05 22.53 20.88 15.82 0.48 0.7 0.32 0.27 2.27 7.37 23.45
3. Results the comparisons of the coefficient of correlation (R2) and

Mean Squared Error (MAE) show that the ANN model
The results of the above investigations are presented with ANN[17-4-1] has the best performance. This model
and discussed in the following subsections. has only 4 neurons in the single hidden layer. The proce-
ANN Models dure followed in these comparisons was similar to the one
As stated earlier, different configurations of the ANN described in the work [11].
models were tested to effectively and efficiently predict In this work, discussion is limited to the best-perform-
the carbonation efficiency of mineral rocks based on the ing configuration (ANN-[17-4-1]) to save space and time
mineralogical and chemical compositions of the rock of the readers. The performances in training, validation
materials. This testing of different configurations is nec- and testing as well as the post-training regression for the
essary to ensure that the most reliable ANN structure is best-performing ANN configuration is shown in Figures
applied to learn the trends and relationships in the range 1 and 2. As shown in figure 1, the performance during
of data used. The well-trained ANN model, having the the training shows gradual learning of the trend in the
best performance criteria, can then be used to predict the data and the effective prediction of the output, resulting
carbonation efficiency values applicable to the cases and in gradual reduction in error (MSE) as the epoch number
conditions of interest. Therefore, this subsection presents increases. The validation process shows that the network
the results of the training, validation and testing, as well has grabbed the relationship among the data and the
as the performances of the different ANN model config- output without tending to overfit. This culminated in the
urations. Out of all the configurations tested in this study, optimal error value of 8.73 × 10–3 at the 23rd epoch.
33
original experimental outputs (carbonation efficiencies)

at most of the points. In fact, in most of the points,
the predicted outputs wholly overlayed the original
experimental outputs. In the remaining points, it is
visually evident that the ANN predictions provide over
99% coverage of the original experimental output values.
`
This corresponds to the correlation coefficient of above
0.99, shown in Figure 2. Thus, the network model used in
this work is a highly efficient one to predict the output of
carbonation process. As stated earlier, this study will be
among the first set of publications, in the open literature,
to utilize the concept of machine learning to predict and
forecast the carbonation efficiency of rock materials based
Figure 1. Performance of the ANN[17-4-1] model during
on the material contents and experimental conditions.
Training, Testing and Validation processes.
The effect of good training and learning is further
reflected in the regression output of the network. This
is shown Figure 2, where the correlation coefficient is
greater than 99%. This points to the fact the network really
learns and adapts the data well. Thus, the ANN[17-4-1]
is suitable for predicting and forecasting the carbonation
efficiency of mineral rocks based on the mineralogical and
chemical compositions of the rock materials as well as
the other experimental parameters. Other configurations
perform less in terms of the criteria of evaluation (MSE
and R2). Therefore, this well-trained network was used Figure 3. Prediction of the experimental efficiency data
to predict the influences of different parameters on the by the ANN
carbonation efficiency.
Effects of Calcium
Figure 4 shows the pattern of carbonation efficiency
with changing percentages of calcium in the mineral.
Largely, the percent of calcium correlates positively with
the carbonation efficiency. Maximum effect of calcium
was found to be 344% rise in carbonation efficiency at
10% increase in the percentage of calcium. This occurs
at data count of 222 in Figure 4. Further increase in the
amount of calcium to 20% and 30% reduces the effect
on carbonation to 318% and 286%, respectively. Similar
behaviour was noticed at the data count of 237, where the
maximum effect of calcium on efficiency was found to be
248% at 10% increase in calcium amount. This reduces to
246% and 243% upon further increase in calcium amount.
The above goes to show that there is optimum level of
increase in the calcium amount to yield increased carbon-
ation efficiency. Though, further increase in the calcium
also yielded higher efficiency, with reference to the orig-
Figure 2. Regression analysis of the predicted and inal level of the calcium in the mineral, but the marginal
targeted outputs
increase continues to decrease with higher % of calcium.
Carbonation Efficiency Li et al. [12] emphasized that the release of calcium or
Figure 3 shows the prediction of the experimental magnesium from the silicate minerals will serve a great
outputs by the best-performing ANN configuration effect on carbonation yield. This idea emanated from the
(ANN[17-4-1]). The figure shows good matches of the natural carbonation process which involves the weather-
34
ing of magnesium, calcium and iron oxide-based silicate 51% for 10%, 20% and 30% rises in magnesium quantity,
minerals, which then transforms atmospheric CO 2 into respectively. Similarly, it was observed at data count 115,
carbonate minerals [13]. The abundance of Mg/Ca-silicates original efficiency at 36.9% falls to 35%, 29% and 22%
on Earth offers enormous capacity for sequestering CO2 [14]. for 10%, 20% and 30% rises in magnesium quantity, re-
Thus, calcium component of the minerals has great and spectively. Also, at data count 200, original efficiency at
positive influence on the efficiency of the carbonation. 4% falls to 2.34%, 2.32% and 2.31% for 10%, 20% and
30% rises in magnesium quantity, respectively. This con-
sistent behaviour shows that there is a maximum amount
expected of magnesium in carbonation minerals, unlike
the iron and calcium.
Figure 4. Carbonation efficiency with change in %

of calcium.
Effect of iron
The presence of iron bears strong positive correlation
with carbonation efficiency in most of the cases consid- Figure 5. Carbonation efficiency with change in % of iron
ered in this study. This is shown in Figure 5. Also, there is
consistent increase in the efficiency as the iron content of
the mineral increases. The highest predicted performance
was recorded as 1541% at 30% increase in iron content.
This has exceeded the performance of all other mineral
contents. At 10% and 20% rises in calcium content, 526%
and 1039% changes in efficiency were recorded, respec-
tively. This occurred at data count 217 in Figure 5. What
can be inferred from the results are the complex interplay
of fractional composition of the mineral contents. For ex-
ample at data count 221 in Figure 5, where conditions are
similar to that at the count 217, the highest performance
Figure 6. Carbonation efficiency with change in %
recorded was 674% at 30% rise in iron content. Upon of magnesium
close inspection, the discrepancy was attributed to the
relatively higher level of magnesium in the former (data
4. Conclusions
count 217). This seems to reveal the complex interrela-
tionship between the fractional composition of mineral This work has successfully demonstrated the clarity
content and carbonation efficiency. Ramli et al. [7] found of influences played by various divalent cations in the
that iron mining waste was influential in determining car- efficiency of mineral carbonation. By training different
bonation efficiency. configurations of Artificial Neural Network (ANN) to
Effect of magnesium understand the complex roles of mineral constituents in
Figure 6 shows the effects of quantitative changes in the carbonation process, statistical appraisal shows that
magnesium on the carbonation efficiency. It can be ob- ANN[17-4-1] possesses the best performance criteria. This
served that the efficiency drops slightly as the magnesium best-performing network was now employed to study the
content increases. The reason for this is not obvious. This roles of divalent cations (calcium, magnesium and iron)
is unlike the cases with iron and calcium, where the effi- of rock minerals in the efficiency of mineral carbonation.
ciency rises with an increase in their quantities. For exam- It was found that carbonation efficiency largely increases
ple, at data count 15, the carbonation efficiency decreases as the quantity of calcium content increases. Averagely,
from the original efficiency of 72% to 65%, 55% and there is approximately 5% rise in the original efficiency
35
for 10% increase in the quantity of calcium. This reduces Malaysia. Minerals. 8(6), 257.
to 3.4% and 1.6% rises over the original efficiency for 20 [5] Huijgen, W.J.J., Witkamp, G., Comans, R.N.J., 2006.
and 30% increases in calcium content, respectively. Iron Mechanisms of aqueous wollastonite carbonation as
content of minerals offers clear positive correlation to the a possible CO2 sequestration process. Chemical En-
carbonation efficiency. From the global average, there is gineering Science. 61, 4242-4251.
approximately 17% rise in the original efficiency for 10% DOI: https://doi.org/10.1016/j.ces.2006.01.048
increase in the quantity of iron. This changes to 29% and [6] Sanna, A., Uibu, M., Caramanna, G., et al., 2014. A
41% rises over the original efficiency for 20% and 30% review of mineral carbonation technologies to se-
increases in iron content, respectively. This goes to show quester CO2. Chemical Society Reviews. 43, 8049-
iron as a great contributor to the mineral carbonation 8080.
among other divalent cations. The influence of magnesium [7] Ramli, N.A.A., Kusin, F.M., Molahid, V.L.M., 2021.
was found to be mainly negatively correlated to carbon- Influencing Factors of the Mineral Carbonation Pro-
ation, after exceeding an unknown threshold. The global cess of Iron Ore Mining Waste in Sequestering At-
average of the efficiency changes with magnesium content mospheric Carbon Dioxide. Sustainability. 13, 1866.
results in original efficiency rising by 2% at 10% quantity DOI: https://doi.org/10.3390/su13041866
increase and then falls by 3% and 9% for 20% and 30% [8] Ukwattage, N.L., Ranjith, P.G., Li, X., 2017.
increase in magnesium quantity, respectively. The study Steel-making slag for mineral sequestration of carbon
shows that, unlike iron, there is optimum level of increase dioxide by accelerated carbonation. Measurement
in the calcium and magnesium contents to yield increased Journal of the International Measurement Confedera-
carbonation efficiency, following which the marginal in- tion. 97, 15-22.
crease in % of the chemicals continue to result in decrease DOI: https://doi.org/10.1039/c4cs00035h
of efficiency. [9] Hanspal, N.S., Allison, B.A., Deka, L., et al., 2013.
Artificial neural network (ANN) modeling of dynam-
Conflict of Interest ic effects on two-phase flow in homogenous porous
media. Journal of Hydroinformatics. 15(2), 540-554.
There is no conflict of interest.
DOI: https://doi.org/10.2166/hydro.2012.119
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ronmental Science & Technology. 48, 5163-5170. [12] Li, J., Hitch, M., Power, I.M., et al., 2018. Integrated
DOI: https://doi.org/10.1021/es405449v Mineral Carbonation of Ultramafic Mine Deposits—
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36

ARTICLE
Assessment of Geotechnical Properties of Laki Limestone for Coarse
Aggregate, Nooriabad, Jamshoro Sindh, Pakistan
Sumaira Asif Khan Adnan Khan*
Department of Geology, University of Karachi, Karachi, Sindh, Pakistan
Article history Present study is aimed at assessment of geotechnical properties of Laki

Received: 21 March 2022 limestone as coarse aggregate which is being quarried in Nooriabad
area, Sindh, Pakistan. Coarse aggregate samples (n=20) of limestone
Revised: 23 April 2022 were collected for the evaluation of physico-mechanical properties of the
Accepted: 28 April 2022 aggregate. Petrographic analysis revealed that the aggregate comprises of
Published Online: 30 April 2022 hard, compact, massive, crystalline and fossiliferous limestone. It is devoid
of any reactive silica (chert, chalcedony) and other harmful constituents
Keywords: like clays or organic matter. Average values of specific gravity, absorption,
bulk density, void content and combined index (EI + FI) of collected
Laki limestone samples are 2.5, 2.1%, 1.54 g/cc, 38.55% and 13.04% respectively. The
Coarse aggregate values of specific gravity (2.3-2.9), absorption (0-8%), bulk density (1.28
Geotechnical properties g/cc-1.92 g/cc) and void content (30%-45%) are varying within the range
of normal weight aggregate as per American concrete institute (ACI)
Nooriabad
specifications. On the other hand, absorption values of aggregate samples
are slightly higher (2.1%) than the reference range (2%) but meet other
requirements. Mechanical properties including aggregate impact value
(8.58%), aggregate crushing value (26.66%), Loss Angeles abrasion value
(24.77%), sodium sulfate soundness (4.72%), water soluble sulfate (0.006%)
and water soluble chloride (0.005%) are found to be within corresponding
guidelines set by ASTM. On the other hand, average carbonate content
is found to be 89.64% indicating that Laki limestone is of slightly low
purity. Except absorption, all physical and mechanical properties lie within
specified ranges. It is concluded that Laki limestone is suitable for use as
road aggregate and concrete mix design.
1. Introduction It occupies major volume (up to 80%) of concrete [2].

Strength and durability of concrete is particularly a func-
Coarse aggregate is the essential raw material for all tion of coarse aggregate [3]. Any geological material can
[1]
types of construction i-e concrete and asphalt work . be utilized as construction aggregate, if it meets end use
Adnan Khan,
Department of Geology, University of Karachi, Karachi, Sindh, Pakistan;
Email: adkhan@uok.edu.pk
37
specifications [4]. Limestone is hard and durable rock to In sedimentary rocks, limestone and dolomite are
be used as an aggregate. The physico-chemical properties generally good source of crushed stone. However, some
of aggregate material depend upon the geologic origin limestone and dolomite may be soft, friable and absorp-
and mineral composition of the source including its sub- tive which may result in poor quality of aggregates. Chert,
sequent weathering and alteration. Aggregate charac- chalcedony, jasper, flint and all other cryptocrystalline
terization can be divided into three categories including silica as well as holohyaline material can cause adverse
physical properties, mechanical properties and harmful chemical reaction when used in cement concrete Moreo-
contaminants. Limestone and dolomite are considered as ver, due to high surface energy and weak internal structure
hard and durable for use as an aggregate. Limestone qual- these are highly reactive. Hard and dense sandstone can
ity for aggregate can be determined by several geological also be used as aggregate material for use in construction.
factors such as waste content, dolomitization level and Construction industry is the single largest user of ag-
degree of folding and faulting. There are many types of gregate in Pakistan. The specifications for aggregates to
sandstone which are too porous and weak to be used other be used in concrete work are more precise than other uses.
than construction filler material. However, relatively old Aggregate quality has significant importance as it affects
and more indurated sandstone give higher strengths. Due the performance, durability and mechanical properties of
to this reason, this type of sandstone may also be suitable concrete [8,9]. If aggregate satisfies these specifications than
as aggregate. On the other hand, igneous rocks usually it almost meets all requirements for other uses. Aggre-
produce strong aggregates with high skid resistance and gate characterization can be divided into three categories
hence are suitable for road surfacing, sub base material including physical properties, mechanical properties and
and aggregate base course in road construction. Igneous other harmful contaminants.
rocks are also good for railway ballast due to their high Physical properties of aggregate include gradation, par-
strength and attrition resistance [5]. Igneous rocks are com- ticle shape, surface texture, porosity, pore structure, spe-
monly used as construction aggregates in areas of igneous cific gravity and change in volume which may affect the
terrain and shield areas. Igneous rocks are hard and dense use of aggregate in concrete mix. Aggregates which are
hence excellent source of aggregate. Some volcanic igne- hard, durable and free from fractures are suitable for use
ous rocks are too porous. Others containing volcanic glass in cement concrete and other constructions. On the other
and siliceous material are highly reactive to use as an hand, particles that are friable, soft, highly fractured and
aggregate. Pyroclastic material such as volcanic ash and having smooth surfaces are not suitable for used as con-
volcanic tuff might be unfit as an aggregate directly but struction aggregate. It is important to understand the ge-
can be used after heating as they become compacted and ology of resource area, production process and reference
cemented by this process. Metamorphic rocks can also be methods for the evaluation of aggregates suitability to be
used as an aggregate material. The factor affecting their used in construction. Mineralogical characters of coarse
suitability for use as an aggregate is type of parent rock, aggregate play fundamental role on making good quality
degree and type of metamorphism and the subsequent al- aggregate [10].
teration and weathering [6,7]. Chemical properties of aggregate affect the strength
Naturally occurring aggregate deposits (either sand and and durability of cement concrete as well as the bitumi-
gravels or rock) all are formed by geological processes. nous work. The presence of certain contaminants can pre-
The physical and chemical properties of aggregates result vent the cement from hydrating or bitumen from adhering
from the geologic origin and mineral composition of the to the aggregate [11]. Particles containing deleterious ma-
potential source and its subsequent weathering and altera- terial, which may react with cement concrete, are harmful
tion. Most of the aggregate properties related to the grain for use in concrete and other construction work.
size, texture, mineralogy, pore spaces and weathering prod- Rapidly growing urbanization and ongoing CPEC
ucts are observed and described by geological methods. (China Pakistan Economic Corridor) projects intend to
Pakistan is mainly a sedimentary terrain where lime- increase the demand of construction raw material includ-
stone is the most common and widely exposed rock avail- ing aggregates in Pakistan. Characterization of aggregate
able throughout the country. Hence, it is the most com- is essential for selection of good quality and performance
mon rock used in construction industry as construction bound aggregate for construction purpose [12]. Laki lime-
aggregate. Aggregates are mainly produced by quarrying stone (Eocene age) which is occurring in Nooriabad area
in Pakistan. After rock quarrying, crushing is performed is being quarried for used as construction aggregate in
for the classification of aggregate into various appropriate Karachi and adjoining areas. However, the suitability and
sizes for multiple uses. in-service performance assessment of Laki limestone as
38
coarse aggregate has not been studied so far which may standard [15]. Aggregate samples were reduced to testing
lead to huge economic loss and life threaten in the future. size according to ASTM C702 for performing different
Therefore, this study is aimed at assessment of engineer- tests. The testing was divided into two parts (a) physical
ing properties of Laki limestone for its use in concrete and (b) mechanical.
mix design and asphalt work.
Study Area
Nooriabad is located in the vicinity of eastern part of
Kirthar Basin where limestone of Laki Formation (Eocene
age) is exposed as hills and ridges (Figures 1 & 2). Laki
Formation is comprised of three members mainly Sohnari,
Laki and Tiyon. This Laki series was subdivided into ba-
sal Laki laterite (8 m), Meting limestone (45 m), Meting
shale (30 m) and Laki Limestone (70 m-200 m) [13]. This
formation contains micro fossils of foraminifera which
suggest that the age of Laki Formation is early to middle
Eocene. Structurally, Nooriabad is located in the synclinal
valley formed by the erosion of limestone. Rocks in study
area are highly deformed due to the occurrence of major
folded structures. Study area is highly deformed by major
Figure 2. Samples location map.
anticlines and synclinal structures. Furthermore, Nooria-
bad is located in synclinal part of area. It is causing run off
2.1 Physical Properties of Aggregate
from adjacent hills towards the base area. Locally this area
has two major faults i.e. Surjan and Jhimpir which occur Following tests were performed for the examination of
around study area. According to Kazmi& Jan [14] further to aggregate physical properties:
the south and west of Lakhra, the north-south Surjan fault
cuts across the Quaternary deposits. West of Jhimpir, the 2.1.1 Particle Shape Analysis (ASTM D 4971)
southern end of this fault is intersected by the north-west Individual particles of coarse aggregate from specific
trading Jhimpir faults (Figure 1). The intersection of two sieves were measured to determine the width to thickness
faults is characterized by at least four teleseismic events ratio by using Flakiness and Elongation gauge. Flakiness
of shallow focal depth and magnitude between 3-6 [14]. Index, Elongation Index and Combined Index (CI) were
calculated on the basis of specific fractions.
2.1.2 Specific Gravity and Water Absorption (ASTM

C127)
Specific gravity was determined in Oven dried (OD),
Saturated Surface Dried (SSD) and Apparent conditions.
The apparatus required for these tests are wire bucket of
3.35 mm, water tank and sieves of various mesh numbers
(3/8, 1/2, 3/4, 1 and 1.1/2 inches). Following are the for-
mulae of calculating different specific gravity values:
Specific Gravity (OD) =A/ (B-C)
Specific Gravity (SSD) = B/ (B-C)
Apparent Specific Gravity = A/ (A-C)
where,
Figure 1. Geological map of study area. A=Oven dry mass of sample in air
B=Saturated surface dry mass of sample in air
2. Materials and Methods C= Saturated surface dry sample apparent mass in water
Twenty coarse aggregate samples were collected from
2.1.3 Bulk Density (ASTM C 29)
different crush plants operating in Nooriabad area (Figure
2). Samples were collected as per international reference Bulk density and void content were determined by us-
39
ing ASTM C-29 method. Bulk density was determined in ried out for the determination of mineral composition and the
loose and compacted stages. Compacted bulk density was presence of alkali silica reactive material in aggregate.
examined by rodding method. Bulk density was calculated
by using the following formula: 3. Results
M = (G-T) / V All representative samples (n=20) were tested accord-
where, ing to reference standard given by ASTM and the results
M= Aggregate bulk density (kg/m3) have been summarized in Table 1.
G = Mass of the aggregate including measure (kg)
T = Mass of measure (kg) 3.1 Particle Shape Analysis
V = Volume of measure (m3)
Shape and orientation of aggregate particle is necessary
The formula of void content is as follows:
for the production of workable concrete. Flakiness and
Void Content (%) = ([(S×W)-M]×100)/((S×W))
elongation of individual particles were measured for par-
where,
ticle shape analysis. FI and EI varied between 2.0-8.1 and
M = Bulk density of the aggregate (kg/m3)
3.2-18.5 with a mean of 5.65±1.68 and 7.38±3.26 respec-
S = Bulk specific gravity (dry basis)
tively. FI and EI of all the samples are within the specified
W = Density of water (998 kg/m3)
range set by ASTM and NHA as well.
Volume of measure was calculated by using following
formula: 3.2 Specific Gravity and Water Absorption
V = (W-M) / D
where, Specific gravity is used in aggregate strength assess-
V = Volume of measure (m3) ment. It is mainly used in the weight volume calculation
W = Mass of the water, plate glass, and measure (kg) of mix design. Bulk SG values of all samples vary within
M = Mass of the plate glass and measure (kg) the range of 2.46 to 2.57 with a mean of 2.51±0.02. While,
D = Density of the water for the measured temperature (kg/m3) SSD specific gravity values ranges between of 2.51 to 2.64
with average of 2.60±0.03. On the other hand, apparent
2.2 Mechanical Properties SG varies between 2.57-2.69 with a mean of 2.64±0.02.
Specific gravity is the inherent property of material and
For the examination of aggregate mechanical properties
function of parent rock composition which varies place to
following tests are carried out:
place and due to this, limits for specific gravity have not
2.2.1 Aggregate Strength Test been set in the standards [19].
Absorption values of all the samples vary between 0.56
Aggregate strength was determined by conducting to 3.09 with a mean value of 2.10±0.5. As per ASTM,
Aggregate Impact Value (BS-812), Aggregate crushing AASHTO, BS and NHA standards, absorption values
value [15] and Loss Angeles Abrasion Value [16]. These tests should be less than 2% for concrete mixes and asphalt
were used to determine the strength, toughness and abrasion work. Samples have shown absorption values slightly
resistance of aggregate against sudden and repetitive forces. higher than the standard range where only sample 10
shows highest absorption value (3.09%). Absorption is
2.2.2 Aggregate Durability Test the indirect measurement of aggregate porosity [20]. High
values of porosity lead to the serious durability concerns.
Soundness of aggregate was determined for the durabil-
It is used in the calculation of mixing water quantity in
ity evaluation of aggregate. ASTM C 88 [17] standard was
concrete and if it is not absorbed by the aggregates, it can
followed to assess the chemical soundness of aggregate.
cause the decrease in compressive strength of concrete [21].
2.3 Carbonate Content of Aggregate
3.3 Bulk Density
Carbonate content of aggregate was determined to as-
All the samples lie in the range of normal weight
sess the chemical grade and purity of limestone aggregate
aggregate where bulk density values ranges between
using ASTM D4373 [18].
1.45 g/cc-1.61 g/cc with an average of 1.54±0.04 g/cc.
2.4 Petrographic Examination (ASTM C 295) Void contents lie between 34.68%-41.94% with a mean of
38.55±1.97%. Results of bulk density are also used in the
Petrographic examination of limestone aggregate was car- calculation of mix design.
40
Table 1. Aggregate samples testing results.

Loss Sodium Aggregate Aggregate
Specific Specific Specific Water Bulk Void Carbonate Insoluble
Flakiness Elogation Combined Angeles Sulafte Crushing Impact Sulfate Chlorid
S .No Gravity Gravity Gravity Absorption Density Content Content Residue
Index % Index % Index % Abrasion Soundness Value Value(AIV) (%) e (%)
(Apparent) (SSD) (OD) (%) (g/cc) (%) (CaCO3 %) (IR) %
Value (%) Test (%) (ACV) % %
1 2.63 2.61 2.52 1.91 1.46 41.947387 6 7 13 21 5.1 22 6.47 88.86 11.14 0.002 0.002
2 2.65 2.6 2.5 1.92 1.45 41.883768 5 4 9 20 5.3 24 6.68 88.98 11.02 0.007 0.002
3 2.62 2.59 2.49 2.03 1.55 37.626257 8 5 13 18 4.9 26 9.96 89.24 10.76 0.005 0.004
4 2.62 2.6 2.51 2.1 1.48 40.917692 4.5 6 10.5 20 5.6 23 6.89 87.88 12.12 0.013 0.002
5 2.66 2.62 2.5 2.04 1.45 41.883768 7 6.7 13.7 18 5.21 21.78 4.74 91 9 0.005 0.002
6 2.68 2.63 2.56 2.15 1.56 38.940381 4 8 12 23 5.9 21.80 11.13 87.8 12.2 0.001 0.002
7 2.63 2.64 2.53 1.54 1.56 38.216354 4.5 9.3 13.8 27 4.26 24.88 8.45 92.1 7.9 0.003 0.004
8 2.691 2.58 2.57 0.56 1.57 38.788082 6 6 12 20 5.42 22.22 8.68 90.2 9.8 0.014 0.001
9 2.67 2.61 2.53 1.85 1.58 37.424256 5.5 12.03 17.53 23 3.7 19.70 4.25 87.86 12.14 0.002 0.001
10 2.57 2.511 2.47 3.09 1.61 34.687188 2 3.2 5.2 30 3.33 28.15 8.00 89.5 10.5 0.001 0.006
11 2.67 2.63 2.51 2.4 1.51 39.720078 5.8 6.5 12.3 25 4.25 26.2 9.70 87.9 12.1 0.007 0.006
12 2.66 2.6 2.539 2.03 1.57 38.040713 7.6 7.2 14.8 26 4.53 27.85 9.14 89 11 0.008 0.008
13 2.66 2.61 2.51 2.12 1.53 38.921668 6 7 13 26.7 4.56 24.5 8.20 88 12 0.008 0.007
14 2.67 2.6 2.5 2.1 1.56 37.47495 5 8 13 28 4.52 25.3 10.20 88 12 0.006 0.006
15 2.67 2.62 2.53 2.09 1.54 39.008452 8.1 6.2 14.3 27 4.59 28.1 8.20 88.5 11.5 0.007 0.006
16 2.63 2.61 2.51 2.2 1.55 38.123258 7.7 5 12.7 25 5.1 22.68 7.81 89 11 0.007 0.007
17 2.6 2.54 2.461 2.9 1.56 36.484102 3.1 5.9 9 24 5.45 31.65 15.24 89.7 10.3 0.008 0.012
18 2.64 2.58 2.462 2.91 1.58 35.695925 4.1 9.2 13.3 29.84 4.11 23.99 9.77 92.44 7.56 0.015 0.007
19 2.67 2.62 2.535 2.03 1.58 37.547679 5.6 18.5 24.1 30 3.94 24.12 8.01 93.86 6.14 0.005 0.004
20 2.66 2.6 2.51 2.1 1.56 37.724054 7.59 7 14.59 34 4.81 25.40 10.15 93.06 6.94 0.004 0.003
Min 2.57 2.511 2.461 0.56 1.45 34.687188 2 3.2 5.2 18 3.33 19.7016781 4.25 87.8 6.14 0.001 0.001
Max 2.691 2.64 2.57 3.09 1.61 41.947387 8.1 18.5 24.1 34 5.9 31.65 15.24 93.86 12.2 0.015 0.012
Mean 2.64755 2.60005 2.51235 2.1035 1.5405 38.5528 5.6545 7.3865 13.041 24.777 4.729 24.6664453 8.58 89.644 7.735 0.006 0.005
SD 0.02978957 0.0302802 0.0288011 0.52382475 0.0463936 1.9755546 1.68539695 3.26354066 3.65661175 4.4267192 0.67269998 2.81110353 2.37157543 1.87733966 1.8773397 0.0041 0.00283
3.4 Aggregate Strength Tests (ACV and AIV) base is 50%, base course 40%, asphalt & cement concrete
30% [15]. Hence, all the samples of Laki limestone aggre-
Aggregate strength is one of the index parameters to
gate lie within the specifications set by ASTM and NHA.
be used in concrete and road aggregate. Aggregate Impact Evaluation of aggregate durability is essential for determi-
Value (AIV) and Aggregate Crushing Value (ACV) are nation of its resistant to abrasion and polishing [24,25]. AIV
used to determine the aggregate strength and toughness. and LAAV are collectively used to assess aggregate per-
AIV of all the samples varies between 4.25%-15.24% formance and durability [26]. Hence a common pattern of
with a mean of 8.58±2.37% which is within the standard data tends toward the low value of LAAV which indicates
range of 4% to 11% except sample 17 (15.24%). Similar- harder aggregate [27].
ly, ACV of all samples lies between 19.7%-31.65% with a
mean of 24.66±2.81%. Generally, crushing values of ag- 3.6 Soundness
gregates less than 30% are acceptable. However, the low-
Aggregate Soundness value is used to identify either
er the crushing value, stronger will be the aggregates [22]. aggregate is prone to degradation in saturated moisture
Maximum permissible limit for crushing value is 30% and condition, elevated temperature and freezing condition [18].
15% for base and wearing course respectively (Arshad & All collected samples of Laki limestone aggregate show
Qui, 2012). ACV values vary within the range of 19 to 28 soundness values lies between 3.3% to 5.9% with a mean
except sample 17 (31.65%). Sample 17 shows the highest value of 4.7±0.67 % (Table 1). Sample 10 shows low-
AIV and ACV values which are 15.24% and 31.65% re- est (3.3%) while 6 shows the highest (5.9%) soundness
spectively. AIV of aggregate between 10%-20% are clas- values. 12% soundness value is acceptable (with sodium
sified as strong aggregate. Hence, Laki limestone falls in sulphate) for used as aggregate base course material while
strong aggregate class. 10% for use in Portland cement concrete [28]. On the other
hand ASTM allows maximum limit of 18% loss after 5
3.5 Loss Angeles Abrasion Value (LAAV)
cycles (ASTM C88). Soundness is the physico-chemical
Loss Angeles Abrasion Value (LAAV) of Laki lime- disintegration of aggregate which is also used to assess its
stone was determined for assessment of aggregate tough- durability and aggregate should be sound for resistance to
ness [23]. Toughness is the ability of material to show intense weathering condition [29,19,30]. All the samples vary
resistance against impact and abrasion due to traffic load. within specified limits set by ASTM and AASHTO and
Interestingly, all the samples fall within the range of 18%- can be considered as sound.
34% with a mean of 24.77±4.42%. Except S-20 (LAAV =
3.7 Petrographic Examination
34%) all the samples lie in the range of 18%-30% for
LAAV. Recommended value of LAAV for aggregate sub About half of the collected aggregate samples (n=11)
41
of Laki limestone were subjected to petrographic exam-

ination. Aggregate is found to be calcitic in composition
and chemically it is calcium carbonate (Figures 3-6).
Microfossils (Foraminifera) are reported to occur in all
samples which are clearly visible in microscopic study.
Since, fossils are biochemically precipitated, calcite is
more pure as compared to chemically precipitated and
contains homogeneous structures. Hence, it is more stable
and relatively less reactive material toward cement or as-
phalt. Based on grain to matrix ratio, most of the samples
are classified as micrite (Mudstone, less than 10% grain)
while two are termed as Packstone (grain supported) and
one sample (S-9) is Wackstone [30]. It is obvious from the
study that micro fractures also occur in about half of the
samples which is indicator of compressional forces. In Figure 4. Microfossils and organic matter visible in sample 2
sample 5, microfractures are filled with recrystallized lime
mud known as sparite (Figure 5). Micrite is amorphous
material while sparite is crystalline which is relatively more
stable and non-reactive as compared to micrite. Presence of
stylolitic suture also confirms the response of compression-
al tectonic forces which has improved the mechanical and
chemical quality of Laki limestone. Organic matter is also re-
ported in some of the samples which is shown in thin section
as dark brown or black streaks visible both in plane polarized
light and cross nicol mode. Samples manifested the occur-
rence of fractured, non-fractured, micritic, sparitic and stylo-
lite features. All samples have angular to sub angular grains
with fractured surfaces and less than 10% flat and elongated
particles. These are free from clay, chert and any other reac-
tive siliceous material harmful for concrete.
Figure 5. Stylolitic sutures and microfractures Filled with sparite
Figure 3. Microfossils in sample 1 Figure 6. Microfossils and 1 set calcitic cleavage
42
All samples (n=20) of Laki limestone aggregate have 4). This significant correlation is either positive or nega-
chloride content ranging between 0.001%-0.012% with an tive. Pearson correlation with 2 tail level of significance
average of 0.005%. These values are within the specified (0.01 and 0.05) is used. Combined Index shows positive
range given by American Concrete Institute (Table 2). correlation while absorption shows a negative correlation
with SG. Bulk density shows an inverse relation with void
Table 2. Chloride ion (%) limit in concrete. content. On the other hand ACV and AIV shows a positive
Chloride limit in Concrete. correlation with each other and also with combined index.
Maximum chloride ion content in concrete 3.8.2 Test of Normality

(percent by weight of cement)
Category of Two tests of normality (Kolmogorov-Smirnovand
reinforce concrete
Acid-soluble Water Shapiro-Wilk) were run on data by using SPSS software
Water soluble
(ASTM
(ASTM C-1218)
soluble with 5% level of significance (Table 5). The outcome of
C-1152) (ACI 222.1)
these tests revealed that about half of the samples are nor-
Pre-stressed (or Post- mally distributed.
0.08 (40%) 0.06 (40%) 0.06 (40%)
tensioned)
Non-prestressed (Wet
0.1 (50%) 0.08 (53%) 0.08 (53%) 3.9.3 Cluster Analysis
condition)
Non-prestressed (Dry Data are classified into two groups with the help of
0.20 (100%) 0.15 (100%) 0.15 (100%)
condition) cluster analysis (Figure 7). Parameters including specif-
Sulfate content in all collected samples are ranging from ic gravity (OD, SSD, and AP), combined index (FI and
EI), soundness, IR and sulfate are gathered in one group.
0.001%-0.015% with an average of 0.006%. These values
On the other hand, absorption, bulk density, LAAV, AIV,
are below the permissible limit given by ACI (Table 3).
ACV, carbonate and chloride content are combined in oth-
Table 3. Recommendation for normal weight concrete er group. As discussed above the correlation between CI
subject to sulfate attack (ACI 201). and SG is linear and relationship between soundness and
Water Water bulk density is inverse. Hence, it can be concluded that in
soluble soluble Water cluster I, all the parameters have a direct relationship with
Sulphate
sulfate in sulfate Cement type cement each other while, in cluster II, parameters are inversely
exposure
soil/rock in water ratio
proportional to each other.
(%) (ppm)
Mild 0.10 150 - -
Type II
IP(MS)
Moderate 0.10-0.20 150-1500 IS(MS) 0.5
Type II +
Pozzoloan
Type V
Severe 0.20 1500 Type II + 0.45
Pozzoloan
3.8 Statistical Analysis

Aggregate testing data were also analyzed statistically
by using SPSS software. SPSS is a software which is used
for data management and to represent the data statistically.
Pearson correlation, cluster analysis and test of normality
were run on the results of collected samples.
Figure 7. Cluster analysis of the data.
3.8.1 Pearson Correlation
Pearson correlation is run on results data to determine
4. Discussion
the significant correlation among all parameters (Table Aggregate of Laki limestone is suitable in terms of phys-
43
Table 4. Pearson correlation at level of significance 0.01 and 0.05.

Correlations
W. Abs Bulk D (g/ C.Index LAAV Sound- AIV CaCO3 SO4

SG (App) SG (SSD) SG (OD) Fl (%) EI (%) ACV (%) IR (%) Cl (%)
(%) cc) (%) (%) ness (%) (%) (%) (%)
P.Corre 1 .665** .705** –.591** –.066 .451* .407 .571** –.027 .152 –.439 –.164 –.023 .023 .131 –.374
SG(App)
Sig. (2-tailed) .001 .001 .006 .781 .046 .075 .008 .910 .523 .053 .490 .923 .923 .581 .105
P.Corre .665** 1 .589** –.460* –.368 .504* .397 .586* –.131 .172 –.500* –.333 –.021 .021 –.137 –.395
SG (SSD)
Sig. (2-tailed) .001 .006 .041 .110 .024 .083 .007 .581 .468 .025 .151 .929 .929 .565 .085
P.Corre .705** .589** 1 –.789** .029 .345 .313 .438 –.161 .228 –.462* –.254 –.100 .100 –.103 –.530*
SG (OD)
Sig. (2-tailed) .001 .006 .000 .902 .137 .179 .053 .499 .333 .040 .280 .674 .674 .666 .016
P.Corre –.591** –.460* –.789** 1 .161 –.414 –.133 –.309 .391 –.306 .500* .338 –.019 .019 –.123 .618**
W.Abs (%)
Sig. (2-tailed) .006 .041 .000 .498 .070 .577 .185 .088 .189 .025 .145 .937 .937 .605 .004
P.Corr –.066 –.368 .029 .161 1 –.218 .296 .164 .610** –.523* .288 .402 .248 –.248 –.058 .351
Bulk.D(g/cc)
Sig. (2-tailed) .781 .110 .902 .498 .356 .205 .490 .004 .018 .218 .079 .293 .293 .809 .129
P.Corr .451* .504* .345 –.414 –.218 1 –.011 .451* –.136 .152 –.141 –.250 .018 –.018 .046 –.137
F.I(%)
Sig. (2-tailed) .046 .024 .137 .070 .356 .963 .046 .569 .523 .553 .289 .941 .941 .848 .564
E.I P.Corr .407 .397 .313 –.133 .296 –.011 1 .887** .318 –.369 –.287 –.135 .471* –.471* –.115 –.145
(%) Sig. (2-tailed) .075 .083 .179 .577 .205 .963 .000 .172 .109 .220 .569 .036 .036 .629 .541
C.I P.Corr .571** .586** .438 –.309 .164 .451* .887** 1 .221 –.259 –.321 –.236 .429 –.429 –.082 –.193
(%) Sig. (2-tailed) .008 .007 .053 .185 .490 .046 .000 .349 .269 .168 .317 .059 .059 .732 .415
LAAV P.Corr –.027 –.131 –.161 .391 .610** –.136 .318 .221 1 –.588** .356 .290 .455* –.455* –.105 .401
(%) Sig. (2-tailed) .910 .581 .499 .088 .004 .569 .172 .349 .006 .123 .214 .044 .044 .661 .080
P.Corr .152 .172 .228 –.306 –.523* .152 –.369 –.259 –.588** 1 –.157 .228 –.240 .240 .239 –.184
Soundness (%)
Sig. (2-tailed) .523 .468 .333 .189 .018 .523 .109 .269 .006 .509 .333 .309 .309 .310 .436
P.Corr –.439 –.500* –.462* .500* .288 –.141 –.287 –.321 .356 –.157 1 .683** .044 –.044 .058 .795**
ACV(%)
Sig. (2-tailed) .053 .025 .040 .025 .218 .553 .220 .168 .123 .509 .001 .855 .855 .808 .000
P.Corr –.164 –.333 –.254 .338 .402 –.250 –.135 –.236 .290 .228 .683** 1 .073 –.073 .153 .655**
AIV(%)
Sig. (2-tailed) .490 .151 .280 .145 .079 .289 .569 .317 .214 .333 .001 .758 .758 .520 .002
P.Corr –.023 –.021 –.100 –.019 .248 .018 .471* .429 .455* –.240 .044 .073 1 –1.000** .066 –.022
CaCO3 (%)
Sig. (2-tailed) .923 .929 .674 .937 .293 .941 .036 .059 .044 .309 .855 .758 .000 .782 .925
P.Corr .023 .021 .100 .019 –.248 –.018 –.471* –.429 –.455* .240 –.044 –.073 –1.000** 1 –.066 .022
IR(%)
Sig. (2-tailed) .923 .929 .674 .937 .293 .941 .036 .059 .044 .309 .855 .758 .000 .782 .925
P.Corr .131 –.137 –.103 –.123 –.058 .046 –.115 –.082 –.105 .239 .058 .153 .066 –.066 1 .199
Sulfate (%)
Sig. (2-tailed) .581 .565 .666 .605 .809 .848 .629 .732 .661 .310 .808 .520 .782 .782 .401
P.Corr –.374 –.395 –.530* .618** .351 –.137 –.145 –.193 .401 –.184 .795** .655** –.022 .022 .199 1
Chloride (%)
Sig. (2-tailed) .105 .085 .016 .004 .129 .564 .541 .415 .080 .436 .000 .002 .925 .925 .401
**. Correlation is significant at the 0.01 level (2-tailed).
*. Correlation is significant at the 0.05 level (2-tailed).
44
Table 5. Statistical variables showing Normal Distribution of data at Level of Significance (LOS) 5%.
Tests of Normality
Kolmogorov-Smirnova Shapiro-Wilk
Statistic Df Sig. Statistic Df Sig.
Specific Gravity (Apparent) .212 20 .019 .915 20 .080
Specific Gravity (SSD) .249 20 .002 .843 20 .004
Specific Gravity (OD) .134 20 .200* .959 20 .532
Water Absorption (%) .227 20 .008 .837 20 .003
Bulk Density (g/cc) .231 20 .006 .862 20 .008
*
Flakiness Index % .125 20 .200 .958 20 .506
Elongation Index % .225 20 .009 .788 20 .001
Combined Index % .215 20 .016 .867 20 .010
*
Loss Angeles Abrasion Value (%) .110 20 .200 .964 20 .628
*
Sodium Sulfate Soundness (%) .109 20 .200 .983 20 .970
Aggregate Crushing Value (ACV) % .102 20 .200* .963 20 .615
Aggregate Impact Value
.148 20 .200* .935 20 .188
(AIV) %
Carbonate Content
.188 20 .062 .854 20 .006
(CaCO3 %)
Insoluble Residue (IR) % .188 20 .062 .854 20 .006
Sulfate (%) .195 20 .045 .914 20 .077
Chloride (%) .169 20 .137 .909 20 .060
ical and mechanical properties. Flakiness and elongation LAAV, AIV and ACV are found within the reference range
indices values are less than 15%. Other parameters of aggre- set by ASTM, AASHTO, BS and NHA. Mineralogically,
gate suitability including LAAV, AIV, ACV and soundness Laki is micritic limestone and chemically it is low purity
are also found within the specified range set by ASTM, grade. Aggregate of Laki limestone is lies in the category
AASHTO, BS and NHA. Specific gravity of all the samples of normal weight aggregate. Hence, it is concluded that
lies within the range of limestone. On the other hand, only Laki limestone aggregate is suitable to be used as coarse
results of water absorption are slightly higher values than aggregate material in cement concrete. It is also suitable
the reference range but samples meet other requirements as for used in road construction for aggregate sub base, ag-
other physical and mechanical properties lie within the spe- gregate base course and asphaltic base course material.
cific ranges. Laki limestone has also been tested for chemical
properties and mineral composition. Data revealed that Laki Author Contributions
limestone is of relatively low chemical purity and mainly
First author has executed the conceived idea of this
micritic in nature which contains lime-mud associated with
organic matter. Micro fractures are also obvious in response project. Literature review, sampling, analysis and write
to compressional tectonics in study area. Bulk density of all up has been carried out by the first author. Study concept
the collected aggregates also lies within the range of normal is created by co-author and supervised. Sample analysis
weight aggregate. and data interpretation has been cross checked by co-au-
thor. Review of paper, corrections and formatting in the
5. Conclusions template and submission to the journal as corresponding
All the collected samples (n=20) of Laki limestone author has been carried out by co-author.
were tested for the evaluation of Physico-chemical and
Conflict of Interest
mechanical properties, mineral composition and chemical
purity. All the strength parameters of aggregate including It is declared that there is no conflict of interest.
45
Funding [10] ASTM C295/C295M-19, 2019. Standard Guide for

Petrographic Examination of Aggregates for Con-
This project has been carried out by self financing.
crete, ASTM International, West Conshohocken, PA.
Acknowledgments https://www.astm.org.
[11] Lesueur, D., Petit, J., Ritter, H.J., 2013. The mecha-
I am thankful to Prof. Dr.Viqar Husain, Former Dean nisms of hydrated lime modification of asphalt mix-
Science and Chairman Department of Geology, University tures: a state-of-the-art review. Road materials and
of Karachi, for his technical guidance.I wish to express pavement design. 14(1), 1-16.
my deepest gratitude to Mr. Kazim Mansoor, CEO, Soil- [12] Ahsan, N., Baloch, I.H., Chaudhry, M.N., et al.,
mat Engineers, Mr. Muhammad Salman, Assistant Materi- 2000. Strength Evaluation of Blends of Lawrencepur,
al Engineer, ASF City and Mr. Syed Shahrukh Ali, Oper- Chenab andRavi Sands with Lockhart and Margala
ations Manager, Soil Testing Services (STS) for technical Hill Limestones for use in Concrete. Special Issue
support and providing lab testing facilities. I am deeply Pak. Muse. Nat. Hist.Pakistan Science Foundation.
grateful to my beloved husband Mr.Zubaid Saeed for his pp. 213-240.
technical and moral support throughout my research work. [13] Shah, S.I., 2009. Geological Survey of Pakistan.
Stratigraphy of Pakistan. 22, 245-273.
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47

ARTICLE
A Typical Sublithospheric Mantle beneath the Tello Region, SE-
Ngaoundéré (Cameroon Line)
Nguihdama Dagwai1* Kamgang Pierre2 Mbowou Gbambié Isaac Bertrand3 Chazot Gilles4
Ngounouno Ismaïla3
1. École Normale Supérieure, Université de Maroua, Cameroun
2. Département des sciences de la Terre, Faculté des Sciences, Université de Yaoundé I, Yaoundé, Cameroun
3. École de Géologie et d’Exploitation Minière (EGEM), Département de Mines et de la Géologie, Université de
Ngaoundéré, Meiganga, Cameroun
4. Université Européenne de Bretagne, Brest, France
Article history Peridotite xenoliths, raised to the surface by alkaline basalts or kimberlites,
Received: 29 March 2022 provide us direct information on the processes and composition of the upper
mantle. They are the major source of information on the state of stress,
Revised: 29 April 2022 pressure and temperature in the deep mantle. They are thus a source of
Accepted: 05 May 2022 petrological and geochemical information that is generally not available on
Published Online: 12 May 2022 the Earth’s surface. Fresh spinel-lherzolite xenoliths exhibit a protogranular
components of the Tello volcano. The Tello is the continental sector of
Keywords: the Cameroon Line, located in the South East of the town of Ngaoundéré
at 75 km approximately between (N7° 13’, N7° 14’) and (E13° 40’ and
Spinel-Lherzolite xenoliths E13° 60’). Minerals’ composition of the xenoliths is ~64% olivine, ~24%
Protogranular orthopyroxene, ~11% clinopyroxene and ~1% spinel. Significant variation
Sublithospheric mantle in (Cr/Cr + Al) of the system shows the reciprocal nature of the spinel
solution.The Tello spinel lherzolites show internal chemical homogeneity
Tello
and represent a normal upper mantle. Their mineral chemistries suggest
Cameroon line equilibrium condition of 830° - 925° and 1.4 GPa-2.3 GPa. These data
suggest that there is good correlation bracket between increasing activity
of Al2O3 and decreasing of practionning of TiO2 into spinel. The AlIV and
AlVI contents vary by 0.05-0.2 and 0.03-0.2 respectively. The majority of
samples caracterise the lithospheric mantle.
1. Introduction tectono-magmatic alignment oriented N30°E, from the

[1]
The “Cameroon Volcanic Line” (LVC) is an active island of Pagalù to Lake Chad . This line is a major
Nguihdama Dagwai,
École Normale Supérieure, Université de Maroua, Cameroun;
Email: da_nguihdama76@yahoo.fr
48
geological structure in Central Africa whose impor- cliff (Mbé), which is a fault mirror 600 m high, where
tance can be compared to the “Rift-Valley system” of several directions interfere. The intense fracturing of the
East Africa [2]. This chain of intraplate volcanoes cov- rocks in the Ngaoundere area is attributed to a NW-SE
ers more than 1600 km long [3] by 100 km wide [4]. It direction compression probably of Cretaceous age [5], and
thus offers the particularity of being one of the few followed by other phases of creative deformations of the
magmatic entities built at the same time in the oce- current reliefs. Tectonic movements responsible for the
anic and continental domains [1] . Structurally, field first Adamaoua uprising took place in Cenomania [6]. The
observations, interpretation of aerial photographs [4] region was then subjected to tectonic compression forces
have made it possible to identify major fracture directions that resulted in significant setbacks, including the South
or major lineaments among which one has the direction Adamaoua dextre, which gives its current shape, the horst
N70°E or direction Adamaoua. The geomorphology of the and grabens model, due to fractures and compressions [7].
Tello is characterized by the presence of volcanic mate-
rial ejected from the crater just at the external limits. The
3. Analytical Methods
cones are generally open on the sides. The specific case of The mineral phases of the Tello xenolites were carried
the fall is open on the SSW side marked by the presence out under the conditions on the Cameca SX 100 micropro-
of a flaring of the crater setting up a laccolite-shaped cave be of the West Microsonde service in Brest (France). The
(Figure 1). The cave is generally marked along the sides test conditions were 15 kV for the acceleration voltage,
by the presence of mantle xenoliths well formed and well for currents of 10 nA or 20 nA depending on the resistance
encrusted in the basalts. Tello xenolites are fragments of of the minerals to the electron beam. The samples ana-
mantellic rocks carried by the magma to the surface dur- lysed are thin strips of rocks of different types (xenoliths)
ing the volcanic eruption. and the analyses are carried out on polished sections in the
European University of Bretagne, Brest, France at service
microsonde west. Before each run, the samples are carbon
metallized. Then a very fine electron incident beam comes
into contact with the sample. Radiation is then analyzed
by spectrometers that each explores a range of precise
wavelengths. It is possible to make a quantitative analysis
of a given element if the spectrometer is fixed at the corre-
sponding characteristic wavelength.
4. Results
4.1 Petrography
At Tello, the cave is generally marked along the flanks by the
Figure 1. Location of the ultramafic xenoliths of the study
area from the Hosséré Addi (Tello) and from the other sectors presence of well-formed mantle xenoliths, well embedded
of the Cameroon Volcanic Line and the Adamawa Plateau in the basalts. The xenoliths size is varying between ten and
thirty centimeters along the sides of the caves (Figure 2a).
Tello (To) spinel peridotites have a coarse grained tex-
2. Geological Setting
ture. Kernels with curvilinear boundaries are disseminated
The structures of the Adamaoua plateau are locally cov- in mesostasis. The texture is protogranular [8]. The silicates
ered with more or less altered volcanic formations. Obser- of xenoliths are composed of orthopyroxene, clinopyrox-
vations of these structures from aerial photographs [5] on ene, olivine, and spinel. The microscopic observation of
gneissic series and veins of volcanic rocks have made it Tello’s thin blade shows large minerals (3 mm to 4 mm)
possible to highlight other dominant directions on the EW and gives the blade a granoblastic texture. The minerals
plateau in its West part and N170°E in its East part. All the observed are orthopyroxen (Opx), clinopyroxen (Cpx),
magmatic occurrences were set up in the pan-African sub- spinel (Sp) and olivine (Ol) (Figure 2b).
stratum rich in calcalkaline granitoids and sometimes cov-
ered by volcano-sedimentary formations of Paleozoic age 4.2 Mineral Chemistry
of the Mangbéi type or by Cretaceous sedimentary forma-
4.2.1 Olivine
tions of Mamfé and Bénoué [6]. One of the morphological
features of the region is represented by the Ngaoundere Olivine has a high forsterite content (91 < Fo < 92).
49
Figure 2. Thin sections of peridotites observed with optical microscope under crossed nicols. (cpx = clinopyroxene, ol=
olivine, opx =orthopyroxene and sp = spinel, abbreviation [9] (a) and macro views of the xenoliths (b).
Table 1 continued
The concentration by weight of NiO is between 0.3% and Si 0.991 0.997 0.998 0.990
0.5% (Table 1). There is a positive correlation between data/Point 139 /1. 143 /1. 140 /1. 162 /1.
NiO and the forsterite content of olivine. Fe2+ 0.159 0.160 0.157 0.156
Mn 0.003 0.002 0.003 0.002
Table 1. Olivine compositions (wt% and a.p.f.u. on the
Mg 1.846 1.831 1.834 1.852
basis 4 oygens)
Ca 0.001 0.003 0.001 0.001
data/Point 139 /1. 143 /1. 140 /1. 162 /1.
Ni 0.009 0.007 0.008 0.008
SiO2 41.08 41.18 41.23 40.95
Fo 91.95 91.87 91.98 92.10
TiO2 0.00 0.03 0.01 0.00
Fa 8.05 8.13 8.02 7.90
Al2O3 0.02 0.04 0.01 0.02
Cr2O3 0.00 0.00 0.01 0.00
4.2.2 Clinopyroxene
FeO 7.87 7.90 7.74 7.73
MnO 0.15 0.11 0.16 0.12 The compositions of the clinopyroxenes (En 48-49
MgO 51.34 50.75 50.82 51.35 Wo47-48Fs2-3) of Tello (b) fall into the field of diopside.
CaO 0.04 0.13 0.05 0.02 Their TiO2 levels are less than 0.55%, and those of Al2O3
NiO 0.44 0.35 0.41 0.40 vary between 5.88%-6.27%. Clinopyroxene is character-
Na2O 0.00 0.00 0.00 0.00 ized by a high value in Mg# 98%, that of orthopyroxene
P2O5 0.00 0.05 0.00 0.00 and olivine. Their AlVII/AlIV ratio varies between 1.11 and
Total 100.93 100.54 100.44 100.58 1.92 (Figure 3) [10]. The TiO2 contents range from 0.17
50
wt% to 0.30 wt% and those of Al2O3 from 4.29 wt% to 4.49 4.2.3 Orthopyroxene
wt% (Table 2). These diopside crystals are Cr-rich with the Orthopyroxenes (Wo 0.8-1.0En 91Fs 7.2) have 2% Al 2O 3
values of Cr# [Cr# = 100 × atomic Cr/(Cr + Al)] (17.29 - and Cr2O3 levels ranging from ~0.3 to 0.8% (Table 3).
19.91) typical of Cr-diopside [11]. The clinopyroxene is Figure 2 [10] with the compositions of Mg-enstatite (Mg# =
characterized by Mg# [Mg# = 100 × atomic Mg/(Mg + 90.6 - 92.4; En88.7-89.4Wo1.2-1.5Fs10.1-9.1) have been analyz-
Fe2+)] values of 93 - 94, higher than those of coexisting ed in the lherzolite xenoliths from Hosséré Tello. These
orthopyroxene (see below) and olivine. The values of values are similar to those calculated for the lherzolite
AlVI/AlIV ratio range between 1.1 and 1.3 for the Cr-diop- xenoliths from Spinel-lherzolite xenoliths from the Aritain
side crystals from Hosséré Addi xenoliths. Volcano, NE-Jordan [12] and significant works on the man-
tle xenoliths sampled along the Cameroon Volcanic Line.
The XMg value varies in the same range as olivine.
4.2.4 Spinel
Spinel crystals display homogenous compositions with
Mg# and Cr# ranging from 81.1 to 81.9 and from 10.6 to
10.8 respectively (Figure 4). The average composition of
spinel as listed in Table 4 is close to Mg0.7sFe2+0.22All.65Cr0.33
Fe2+0.0204. The XMg value varies from 0.80 to 0.81 and the XCr
Figure 3. Compositions of the pyroxenes analyzed in the value from 0.13 to 0. 14. Al and Cr are relatively reversed
Spinel-Xenoliths of Tello [10] correlated to each other. TiO2 contents are low (~0.10 wt%)
Table 2. Clinopyroxene compositions (wt% and a.p.f.u. on the basis of 6 oxygens)
Data /Point 132 / 133 / 135 / 148 / 149 / 150 / 151 / 146 / 154 / 155 /
SiO2 53.20 53.15 53.09 52.72 52.64 53.30 53.40 53.38 53.74 53.40
TiO2 0.28 0.28 0.26 0.25 0.27 0.30 0.25 0.21 0.17 0.21
Al2O3 4.48 4.37 4.29 4.30 4.36 4.49 4.64 4.28 4.39 4.47
Cr2O3 1.56 1.56 1.43 1.48 1.57 1.55 1.66 1.44 1.41 1.61
FeO 2.03 1.94 2.10 2.13 2.21 2.02 1.91 2.18 1.96 1.85
MnO 0.10 0.06 0.07 0.03 0.07 0.06 0.08 0.05 0.10 0.06
MgO 15.88 15.79 15.96 16.01 15.92 15.76 15.63 15.65 15.92 15.38
CaO 21.20 21.12 20.87 21.00 20.79 21.08 20.89 21.23 21.21 21.08
Na2O 0.05 0.06 0.03 0.03 0.00 0.05 0.06 0.01 0.06 0.06
K2O 1.71 1.80 1.80 1.65 1.60 1.83 1.69 1.68 1.73 1.82
Total 100.49 100.13 99.90 99.64 99.42 100.45 100.26 100.14 100.71 99.95
Wo(Ca) 1.89 2.00 2.26 2.23 1.67 1.91 0.47 1.23 1.43 0.88
En (Mg) 0.33 0.13 0.07 0.12 0.70 0.30 1.49 1.07 0.67 1.06
Fs(Fe2+Fe3+Mn) 100.68 100.33 100.12 99.86 99.59 100.63 100.31 100.27 100.85 100.03
Si 1.924 1.929 1.931 1.924 1.924 1.928 1.932 1.937 1.936 1.939
Aliv 0.076 0.071 0.069 0.076 0.076 0.072 0.068 0.063 0.064 0.061
Alvi 0.115 0.116 0.114 0.109 0.112 0.120 0.130 0.120 0.123 0.130
T
Al 0.191 0.187 0.184 0.185 0.188 0.192 0.198 0.183 0.186 0.191
Ti 0.008 0.008 0.007 0.007 0.007 0.008 0.007 0.006 0.005 0.006
Cr 0.045 0.045 0.041 0.043 0.045 0.044 0.048 0.041 0.040 0.046
Fe3+ 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Fe2+ 0.061 0.059 0.064 0.065 0.067 0.061 0.058 0.066 0.059 0.056
Mn 0.003 0.002 0.002 0.001 0.002 0.002 0.002 0.002 0.003 0.002
Mg 0.856 0.854 0.865 0.871 0.867 0.850 0.843 0.846 0.855 0.833
Ca 0.821 0.821 0.813 0.821 0.814 0.817 0.810 0.825 0.819 0.820
Na 0.004 0.004 0.002 0.002 0.000 0.003 0.004 0.001 0.004 0.004
Mg# 0.93 0.94 0.93 0.93 0.93 0.93 0.94 0.93 0.94 0.94
51
Table 3. Orthopyroxene compositions (wt% and a.p.f.u. on the basis of oxygens).

Data /Point 130 /1. 131 /1. 136 / 1. 137 / 1. 138/1 141 /1 157 /1. 147 /1. 152 /1. 153 / 1.
SiO2 56.61 56.75 57.21 57.06 56.68 57.21 56.66 56.78 56.98 56.72
TiO2 0.06 0.08 0.12 0.06 0.04 0.00 0.07 0.04 0.08 0.05
Al2O3 2.56 2.35 2.34 2.38 2.45 2.42 2.32 2.57 2.32 2.34
Cr2O3 0.50 0.40 0.42 0.48 0.43 0.45 0.43 0.51 0.45 0.42
FeO 5.03 4.89 5.05 5.09 4.94 4.92 4.98 4.97 4.91 4.89
MnO 0.10 0.14 0.16 0.11 0.11 0.11 0.16 0.11 0.09 0.08
MgO 34.56 34.99 34.86 34.71 34.43 34.93 34.92 34.86 34.60 35.17
CaO 0.60 0.59 0.50 0.69 0.65 0.49 0.55 0.65 0.49 0.58
Na2O 0.09 0.09 0.10 0.08 0.07 0.12 0.08 0.08 0.08 0.10
Total 100.11 100.28 100.78 100.66 99.81 100.65 100.17 100.58 99.99 100.34
Si 1.929 1.939 1.948 1.946 1.948 1.949 1.939 1.936 1.953 1.935
iv
Al 0.071 0.061 0.052 0.054 0.052 0.051 0.061 0.064 0.047 0.065
Alvi 0.033 0.033 0.042 0.042 0.047 0.046 0.033 0.039 0.046 0.029
Ti 0.001 0.002 0.003 0.002 0.001 0.000 0.002 0.001 0.002 0.001
Cr 0.014 0.011 0.011 0.013 0.012 0.012 0.012 0.014 0.012 0.011
Fe3+ 0.030 0.020 0.000 0.002 0.000 0.001 0.020 0.014 0.000 0.028
Fe2+ 0.115 0.120 0.144 0.143 0.142 0.139 0.123 0.128 0.141 0.112
Mn 0.003 0.004 0.005 0.003 0.003 0.003 0.004 0.003 0.003 0.002
Mg 1.774 1.782 1.770 1.765 1.764 1.774 1.781 1.772 1.768 1.789
Ca 0.022 0.022 0.018 0.025 0.024 0.018 0.020 0.024 0.018 0.021
Na 0.006 0.006 0.007 0.006 0.005 0.008 0.006 0.005 0.005 0.006
K 0.002 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000
Wo (Ca) 1.14 1.11 0.95 1.30 1.24 0.92 1.04 1.22 0.93 1.08
En (Mg) 91.26 91.51 91.38 91.05 91.23 91.68 91.42 91.30 91.64 91.66
Fs(Fe2+Fe3+Mn) 7.60 7.38 7.67 7.65 7.52 7.40 7.55 7.48 7.43 7.26
Table 4. Spinel compositions (wt% and a.p.f.u. on the basis of 32 oxygens).

Data/Point 128 /1 129 / 1 144 / 1 145 / 1
SiO2 0.02 0.36 0.00 0.06
TiO2 0.18 0.21 0.14 0.17
Al2O3 34.64 34.91 35.13 35.01
Cr2O3 32.81 32.67 32.86 33.16
FeO 13.04 13.21 12.94 12.96
MnO 0.12 0.15 0.17 0.12
MgO 17.55 17.34 17.95 17.46
CaO 0.00 0.00 0.00 0.00
Na2O 0.00 0.00 0.00 0.00
NiO 0.20 0.24 0.21 0.24
P 2O 5 0.00 0.00 0.02 0.00
Total 98.59 99.11 99.41 99.17
Fe2O3 (calc) 3.23 2.38 3.50 2.70
FeO (calc) 10.14 11.06 9.79 10.53
Total (calc) 98.90 99.34 99.76 99.44
Si 0.01 0.08 0.00 0.01
Ti 0.03 0.04 0.02 0.03
52
Table 4 continued
Data/Point 128 /1 129 / 1 144 / 1 145 / 1

Al 9.40 9.43 9.43 9.45
Cr 5.97 5.92 5.92 6.00
3+
Fe 0.56 0.41 0.60 0.46
Fe2+ 1.95 2.12 1.86 2.02
Mn 0.02 0.03 0.03 0.02
Mg 6.02 5.92 6.09 5.96
Ca 0.00 0.00 0.00 0.00
Na 0.00 0.00 0.00 0.00
Ni 0.04 0.04 0.04 0.04
Cr# 0.39 0.39 0.39 0.39
and those of Al2O3 are high (up to 55 wt%). The Cr2O3 con- single site ideal solution for Fe-Mg substitution due to in-
tents vary between 12.93 wt% and 13.45 wt% (Table 4). teractions between X and Y sites, called reciprocal effects.
The interactions of the cations (Al. Cr) in the Y sites of
4.2.5 Characterization of Xenoliths Studied Accord-
the spinel with the cations (Fe. Mg) in the X sites can be
ing to Their Areas of Genesis
described by the following reaction:
The AlVI/AlIV ratio, variable between 0.70 and 1.14, is FeAl2O4 + MgCr2O4 = FeCr2O4 + MgAl2O4 [15]
similar to that of the clinopyroxenes of the peridotites of Since spinel is a mineral rich in Cr compared to the
the subcontinental upper mantle of Ngaoundéré [13] and of other phases in which Cr is almost in trace, the ratio (Cr /
the sublithospheric crust [14]. The diagram in Figure 4 be- Cr + Al) sp reflects that of the system and control (Mg /
low, shows the distribution of the different samples in two Mg + Fe2+) sp. Autocorrelation is observed in Figure 5.
categories of cpx; the cpx domain of the lithospheric man- This figure, which shows the reciprocal nature of the spi-
tle and those of the lower crust. The samples from Tello, nel solution, also illustrates a significant variation in (Cr /
Likok and Ganguiré fall within the cpx domain of the lith- Cr + Al) of the system.
ospheric mantle [14], while those of Liri, Maz 1 and 2 fall
within the cpx domain of the lower crust. According to the
diagram in Figure 4 below, the AlIV and AlVI contents vary
by 0.05-0.2 and 0.03-0.2 respectively. No sample falls into
the granulitic xenolith facies domain, nor into the eclogite
and igneous domain facies.
Figure 5. Mg # -Cr # autocorrelation diagram for the spinel

phase. The ophiolite reference is reported after [16] a) Domain
of ultrabasic enclaves (Lherzolites and Harburgites) in basic
lavas b) Domain of ultrabasic rocks in ophiolites [16].
A well-defined domain can be clearly seen for the xeno-
liths studied which is placed above that corresponding to the
ophiolitic massifs ophiolites field after [17]. This is the normal
position of spinel peridotites typical of a lithospheric mantle
sampled by alkaline magma soaked in a few hours. This
Figure 4. Variation of Cr (afu)versus Mg# (a), AlVI versus AlIV characteristic leads us to believe that these peridotites are not
(c) , Ti (afu) and Na (afu)versus Mg# (=100*Fe2+/ Fe2++Mg) (b portions of an ultrabasic body (tectonic scale) in the continen-
and d), samples of lherzolite xenoliths fall within majority the tal crust but that they have a deep origin in the mantle. This
scope of lithospheric mantle [14].
observation is quite similar with that of other xenoliths in
the alkaline basalts of Cameroon [18]. The difference between
4.2.6 Spinel-Bearing lherzolite Xenoliths Origin
the position of xenoliths and ophiolites has been explained
It is well known that spinel cannot be considered a by the kinetics of this exchange reaction. The refractory ele-
53
ments as Cr are enriched in the residue, as demonstrated for 5.2 Comparison between the Trace Elements of
the Cr-rich clinopyroxene from Hosséré Addi xenoliths. Thus Clinopyroxenes of Tello and Other Sectors
the studied spinel-bearing lherzolite xenoliths characterized
by the presence of Cr-diopside represent probably portions of Compared to rare earths elements, the trace elements in
the upper mantle. However, the compositions of olivine and clinopyroxene are almost similar. Weak anomalies in Ba,
spinelle are highly dependent on the degree of fusion char- Nb and Ti and a strong negative anomaly in Pb are ob-
acterized by near constant values of (Mg#)Ol, (Mg#)Sp and served in all the samples of the xenoliths (Figure 7, Table
(Cr#)Sp. On the basis of these data, Hosséré Tello xenoliths 5). The general shape of the spectra follows the same con-
represent a residual sequence resulting from the partial fusion tours except for a slight difference observed at the level of
of a mantellic source. Experiments have shown that the com- the Tello xenoliths. The spectra on the whole are therefore
position of solid solutions such as olivine, is very sensitive homogeneous. Pb depletion in cpx is a function of mobi-
to temperature changes and its constituents could evolve to lization by metasomatic fluids. In fact, it is the character
refractory elements during partial fusion. So an extraction that explains the compatibility of lead with the metallif-
of the melt could leave a residue depleted in highly incom- erous deposits of the continental crust where fluids play a
patible elements (e.g. Na. Al. K. and Ti) and enriched in Cr primordial role [19] after a partial melting of the mantle.
and Ni relative to the most primitive mantle. The range of Ni
contents of olivine of lherzolites from Hosséré Tello confirms
that they are residues of melting. The high Ni (2500 ppm -
4100 ppm) levels in olivine suggest that Hosséré Tello xeno-
liths may have originated from a low degree of fusion (~30%)
from a relatively homogeneous mantellic source.Thus, the
model for portions of the earth’s upper mantle appears ap-
propriate for the origin of the Hosséré Addi spinel-bearing
lherzolite xenoliths.
5. Geochemestry and Geothermobarometry

Figure 7. Multi-element spectra of clinopyroxene from
5.1 The Rare Earths Elements of the Clinopyroxenes the peridotites of the 03 previously stated localities and
of the Samples from Tello Tello peridotites, normalized to the values of the primitive
mantle (Sun and Mc Donough, 1989)
There are significant depletions of zirconium, titanium,
and yttrium relative to elements with similar compatibilities
5.3 Geothermobarometry
(REE) (Table 5). Rare earth spectra differ slightly. In the Tel-
lo sector, two scenarios are clearly distinguished (Figure 6). The use of Bertrand and Mercier thermometers (1985),
The first characterizes clinopyroxenes with LaN enrichment T (B&M), and that of Brey and Köhler (1990), T (B&K),
relative to chondrites and nearly equal Ce, Pr Nd contents. is based on exchanges between orthopyroxen-clinopy-
This reflects the presence of a concavity within the light rare roxen [20]. An equilibrium temperature of approximately
earths. The spectrum of clinopyroxenes at the medium rare 905 °C was estimated for Hosséré Tello’s lherzolite-spinel
earth level is almost linear, reflecting the same Sm, Eu and xenoliths [21]. Geothermometer (Table 6), based on the sol-
Gd contents. A slight depletion of heavy earths is also ob- ubility of Al2O3 in orthopyroxen and spinel, the expression
served. The second scenario is characterized by increasing of the calibrated temperature at the pressure of 1.5 GPa in
pace from La to Lu marking a slight enrichment in heavy and a natural spinel lherzolite system, gives the equilibrium
almost rectilinear rare earths. temperatures of Hosséré Tello’s lherzolite to spinel xen-
oliths from 1215 °C - 1245 °C. The Hosséré Addi (Tello)
xenoliths were probably sampled by the host basalt of the
upper sublithospheric mantle at depths of 25 km to 36 km,
and calculated temperatures are about 200 °C above those
of the oceanic geothermal. The maximum pressure can be
calculated from the composition of the spinel [22] or estab-
lished with the crystalline chemistry data of the clinopy-
Figure 6. Primitive mantle normalized REE patterns in roxene to determine the variability of the pressure during
Clinopyroxene from Tello peridotite xenoliths partial fusion.
54
Table 5. Chemical analyzes of rare earths and trace elements in the Cpx of the different localities
TO-01 TO-02 TO-03 TO-04 TO’2 TO’4 TO’5 TO’6
La 20.963 21.900 19.898 20.750 6.216 6.374 5.539 6.574

Ce 11.174 11.870 11.008 11.157 8.455 8.654 7.875 8.803
Sr 19.779 21.103 20.023 21.249 7.973 8.504 7.368 7.882
Nd 11.516 11.384 10.610 11.096 10.986 11.782 10.787 11.671
Zr 5.596 6.020 5.332 5.878 10.485 11.873 10.914 10.198
Sm 14.616 14.412 12.712 13.528 12.508 14.956 11.693 14.616
Eu 14.214 14.071 13.000 13.411 12.839 14.536 13.071 14.071
Gd 13.795 14.079 12.497 13.545 14.446 14.496 13.123 14.547
Ti 4.201 4.254 4.114 4.248 9.268 8.438 8.589 8.716
Dy 10.301 10.630 9.559 9.971 15.657 15.904 13.679 16.605
Er 6.784 6.621 6.067 6.337 15.356 14.915 13.971 12.775
Yb 4.234 4.449 3.865 4.197 12.671 13.631 13.212 12.246
Lu 4.160 4.160 3.914 3.909 13.827 12.346 12.016 12.757
Table 6. geothermometric estimation (°C) of ultramafic xenoliths

Sample Methode Sample Methode
Lherzolites opx-sp Opx-ca opx-sp Opx-ca
B&M B&K1 B&K2 B&M B&K1 B&K2
834.27 892.11 1187.69 984.24 933.41
849.61 890.10 1117.02 919.86 927.75
869.38 900.89 1119.39 911.48 894.46
846.00 880.45 936.28 962.11
848.87 894.07 1140.33 915.78 950.96
852.36 924.89 921.03 889.01
TO1
TO3 849.19 910.34 932.31 914.09
852.11 919.68 970.39 947.81
856.53 904.37 911.62 890.00
Samples 834.30 902.60 934.81 922.66
831.01 885.53 954.98 910.35
851.31 891.39 936.56 920.89
854.96 869.21
1103.93 865.29 852.13
1112.43 844.68 874.37
1101.90 846.02 865.10
TO2
856.41 898.59
824.67 864.47
843.25 874.08
The xenoliths of the mantle of Hosséré Tello as for 6. Discussion and Conclusions
most of the xenoliths of the Cameroon Line show that
they are peridotites of lherzolithe to spinel, not containing Considering the investigations of trace elements in
plagioclase or garnet and are derived from the spinel sta- single grain, clinopyroxenes provide reliable information
bility field in the mantle which is in a pressure range of ~ about chemical composition. The trace elements compo-
0.8 GPa to ~2 GPa [22,23]. These estimated pressures may sition of clinopyroxene analyzed in spinel-lherzolite xen-
be associated with depths of 30 km to 60 km as reported oliths from Tello is therefore a useful indicator of chem-
for the other Lherzolite spinel [24,25]. ical modification in the mantle. According to Jankovics
55
et al. [14], the samples from Tello, fall within the cpx do- [3] Fitton, J.G., Dunlop, H.M., 1985. The Cameroon
main of the lithospheric mantle. According to the diagram line, West Africa, and its bearing on the origin of
in Figure 4, the Aliv and Alvi contents vary by 0.05-0.2 and oceanic and continental alcali basalt. Earth Planet Sci
0.03-0.2 respectively. No sample falls into the granulitic let. 72, 23-38.
xenolith facies domain, nor into the eclogite and igneous [4] Tchoua, M.F., 1974. Contribution à l’étude
domain facies. The spinel peridotites typical of a litho- géologique et pétrologique de quelques volcans de
spheric mantle is sampled by alkaline magma soaked in a la ̎Ligne du Cameroun̎ (Monts Manengouba et Bam-
few hours. Thus, Figure 4 allows the studied spinel-bear- bouto). Thèse Doct. d’Etat. Univ. Clérmont-Ferrand.
ing lherzolite xenoliths characterized by the presence pp. 337.
of Cr-diopside which represent probably portions of the [5] Dumont, J.F., Toteu, S.F., 1984. Sur deux cycles de
upper mantle [14]. We observe in all the samples of the xen- migmatisation dans la zone mobile panafricaine, au
oliths the weak anomalies in Ba, Nb and Ti and a strong Nord Cameroun, 10 R.A.S.T., Bordeaux.
negative anomaly in Pb (Figure 6). [6] Tchameni, R., Pouclet, A., Penaye, J., et al., 2006.
The slight depletion of rare earths elements in the ana- Petrography and Geochemistry of the Ngaoundéré
lyzed clinopyroxenes (Tello 01, Tello 02, Tello 04, Tello Pan-African Granitoids in Central North Cameroon:
4) compared with the other REE observed in the others Implications for Their Sources and Geological Set-
clinopyroxenes from Tello is indicative of a partial melt- ting. Journal of African Earth Sciences. 44, 511-529.
ing episode. Our results are similar to those described by DOI: http://dx.doi.org/10.1016/j.jafrearsci.2005.11.017
Nkouandou et al. [26], that the general shape of the spectra [7] Le Maréchal, A., 1976. Géologie et géochimie des
follows the same contours except for a slight difference sources thermo-minérales du Cameroun. Travaux et
observed at the level of the Tello xenoliths. The spectra documents ORSTROM, Paris. 59, 1-175.
on the whole are therefore homogeneous. Pb depletion in [8] Mercier, J.C., Nicolas, A., 1975. Textures and fabrics
cpx is a function of mobilization by metasomatic fluids. of upper mantle peridotites as illustrated by xenoliths
In fact, it is the character that explains the compatibility from basalts. Jour Petrol. 16, 454-487.
of lead with the metalliferous deposits of the continental [9] Kretz, R., 1983. Symbols for rock-forming minerals.
crust where fluids play a primordial role [14]. The compo- Amer Miner. 68, 277-279.
sitions of their silicate minerals are typical of equilibrated [10] Morimoto, N., 1989. Nomenclature of Pyroxenes.
Mg-rich olivine. Al-rich enstatite and Cr-diopside in the Canadian Mineralogist. 27, 143-154.
upper mantle. Similar compositions have been recorded [11] Dal Negro, A., Carbonin, S., Domeneghetti, C., et al.,
in minerals of ultramafic xenoliths from other ultramafic 1984. Crystal Chemistry and Evolution of the Clin-
xenoliths domains of the Cameroon Volcanic Line and opyroxene in a Suite of High Pressure Ultramafic
the Adamawa Plateau. Thus, ultramafic xenoliths from Nodules from the Newer Volcanics of Victoria. Aus-
Hosséré Addi represent peridotites sampled from litho- tralia. Contributions to Mineralogy and Petrology.
spheric mantle and hosted in the basaltic lava flowed. The 86, 221-229.
spinel-bearing lherzolite xenoliths show internal chemical [12] Nasir, S., A1-Fuqha, H., 1988. Spinel-Lherzolite Xe-
homogeneity and their mineral chemistries suggest equi- noliths from the Aritain Volcano. NE-Jordan.
librium conditions of 820 °C-1200 °C. [13] Dautria, J.M., Girod, M., 1986. Les enclaves de
lherzolite à spinelle et plagioclase du volcan de Dibi
Conflict of Interest (Adamaoua, Cameroun): des témoins du manteau
anormal. Bulletin De Mineralogie. 109, 275-286.
There is no conflict of interest.
[14] Jankovics, É., Dobosi, G., Embey-Isztin, A., et al.,
2013. Origin and ascent history of unusually crys-
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57

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ARTICLE INFO ABSTRACT

1. Introduction It was the potential of discovering potassium salt (sylvine)

2. Methods and Materials

classical biodegradation of organic matter from the post-

the escaped methane molecules can be caught in hydrate

Figure 5. Measuring the daily methane output with a

In Table 1, Yakimov et al. [21] compiled the average

Table 1. Average chemical composition of the Medee Lake brine

3. Discussion Our deduction is: besides the primary and secondary

diluted the formation water. and Petroleum Geology. 27, 191-214.

Romania. AAPG Bulletin. 10, 1641-1653. 1999-2008.