)7102 ‫المؤتمر الوطني االول للتلوث البحري والمياه الجوفية (طرابلس‬

1st National Conference on Marine and Groundwater Pollution

(1st NCMGP-2017)

Determination of water type in Benghazi Plain aquifers by chemical

and statistical methods
Mohamed S. E. Al Faitouri, and Ahmed M. Muftah
Department of Earth Sciences, Faculty of Science, University of Benghazi- Libya

Abstract
The quality of portable water in Northeast Libya become real problem. As fast growing in
population, the city requests more portable water, especially after the sea water intrusion has
taken place. Moreover, building houses and factories above the main costal aquifers rise the risk
of drinking the groundwater. In this study, the TDS values were varied between 800 – 16038
ppm, with an average of 5290.214 ppm. Calcium and Magnesium ranged between 88-1600 ppm
and 37 – 1459 ppm. Sodium in the groundwater is largely controlled by the saline intrusions,
evaporates and silicate minerals. Sulfate varied between 58- 2544 ppm. The water samples show
that some samples are typically from seawater, while the rest samples are to domain of
evaporation. The present study showed four type of water: 1. Ca-Mg-Cl-SiO4 type, 2. Ca-Mg-
HCO3 type 3. Na-K-Cl-SiO4 type, 4. Na-K-HCO3 type, as proved also by the Cluster analysis.

Introduction
Al Jabal al Akhdar anticlinorium is a part of the northern African-Arabian active margin that had
been evolved following the opening of the Neotethys. This anticlinorium is extending from the
boundary of Benghazi to about 345km to the Northeast, 75km in width and yields 2000m thick of
Upper Cretaceous to Upper Miocene successions. The Cenozoic rocks are, generally, thick on the
flanks of this anticlinorium (e.g. in well A1-36) (Abdulsamad and Barbieri 1999), whereas,
towards the crest, they are thin and interrupted by unconformities. This area is classified into the
mobile province in the north (referred as Al Jabal al Akhdar) and more stable Cyrenaica platform
province in the south by some workers e.g. Elwerfalli et al (2000); El Hawat and Abdulsamad
(2004). These two structural provinces are separated by the hinge line of the Cryenaican fault
system. This line is, approximately, coincident with the major E-W normal faulting outlined from
the subsurface data by El- Arnauti and Shelmani (1985) that delimits the termination of Paleozoic
sub-crop in the north of the Cryenaican fault system.

Stratigraphy
The exposed rocks in the Benghazi region, are, largely, represented by the Benghazi Formation
(Middle Miocene) and the Wadi al Qattarah Formation (Upper Miocene), and covering a large
area in the western and southern parts of Al Jabal al Akhdar region, including the study area,
where there are numerous dolines and other karstic galleries as in Ayn Zayanah, Al Kuwiffia,

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1st National Conference on Marine and Groundwater Pollution
(1st NCMGP-2017)

Bou-Dazirah, Rommel pools and Lethe area Abdelmalik et al., (2007). It represents the last
transgressive cycle of sedimentation which extends from The Middle Miocene up to the Late
Miocene (El Hawat and Salem, 1985, 1987). This transgression came from West and Southwest
forming a shoaling up cycle, onlapping on the older Tertiary formations (Abdel-Gawad et al.,
2008). These two formations are separated by a disconformity surface as indicated by the
regional hard ground (see El Hawat and Abdulsamad, 2004).

Water chemistry
A total of fourteen water samples were collected and physicochemically analysed for the quality
assessment (Fig. 1). The total hardness was within the World Human Organization (WHO) and
the Libyan Specification (LS) except the samples that were taken from the blue lagoon and Ayn
Zayanah. The pH was within the WHO permissible level (6.5 to 8.5) except the blue lagoon and
Ayn Zayanah. total alkalinity(TA), total dissolved solids (TDS), {Sodium (Na+), Calcium (Ca2+),
Magnesium (Mg2+), Potassium (K+), Chloride (Cl−), Bicarbonate (HCO3−), Sulfate (SO4)} were
within the accepted limits of LS and WHO for all location except blue lagoon and Ayn Zayanah.
In all, portable water in Benghazi Plain is relatively unsafe and not fit for consumption.
Therefore, there is need for regular quality control monitoring of portable water to minimize the
risk of related health consequences due to contamination.

Fig. 1: Location map of Benghazi plain shows the sample localities, red circles.

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1st National Conference on Marine and Groundwater Pollution
(1st NCMGP-2017)

Water type and hydrochemical facies evaluation are extremely useful in providing a preliminary
idea about the complex hydrochemical processes in the subsurface. Determination of
hydrochemical facies was extensively used in the chemical assessment of groundwater and
surface water for several decades. This method is able to provide sufficient information on the
chemical quality of water, particularly the origin. However, over the years the methods were
undergone substantial modifications, without changing much on the basic theory behind it. The
first attempt in this direction was made by Hill (1940) and the modified versions by Piper (1944)
and Durov (1948) respectively. However, these modification plots could be drawn only by the
specific software packages.
The consumption of water containing pathogenic organisms or toxic chemicals and the use of
inadequate volumes of water, resulting in poor hygiene, pose serious risks to human health. In
addition, the physical condition of water (color, taste and odor) might render it undrinkable as it
can be rejected by end users. For this reason, water quality assessment and continuous monitoring
are of utmost importance.
For the period indicated, water samples were analyzed for pH, conductivity (EC), total alkalinity
(TA), total dissolved solids (TDS), cations (sodium (Na+), calcium (Ca2+), magnesium (Mg2+),
potassium (K+), anions chloride (Cl−), bicarbonate (HCO3−), sulfate (SO4), these data were
summarized in Table 1.

Results and discussion

Water quality
Water quality parameters of the Studied areas are presented in Table 1. Practically all the natural
waters contain dissolved minerals. Some inorganic substances occur relatively frequently in
drinking water in significant concentrations. When water comes in contact with the soil, rocks or
deposits of certain minerals, some of the mineral matter dissolves in it. The studied water
samples were collected during summer 2016. In the present study, the concentrations of the
anions and the cations in some samples are much greater than the drinking water standards. All
the samples were alkaline in nature, with a range of 7.28- 9.23.

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1st National Conference on Marine and Groundwater Pollution
(1st NCMGP-2017)

Table 1: Chemical analysis data (concentration in ppm) of the studied water samples
Location Sample# Ca Mg Na K HCO3 Cl Sio4 TDS EC(µSec/cm) PH
Koeiffyah-well 1 400 268 460 78 360 1489 768 3643 6420 8.70
Sidi Mansower-well-1 2 130 61 104 33 281 319 58 846 1489 8.79
Sidi Mansower-well-2 3 100 37 115 20 268 323 96 875 1564 8.66
Buhmira-2016 4 600 356 805 113 409 2695 720 5493 9800 8.96
Majdob-2016 5 760 389 495 98 256 2482 758 5110 9320 8.81
Habibi-2016 6 560 486 276 78 268 2340 384 4258 8040 8.83
Ayn Zayanah spring 7 1200 1094 2323 196 275 7092 2448 14491 25600 8.62
Ayn Zayanah 8 1400 924 1794 198 281 7447 2304 14208 26300 8.6
Blue Lagoon 9 1600 1459 1886 235 305 8156 2544 16038 28800 9.23
Jabbah 10 480 195 460 39 293 1347 427 3330 6180 9.2
Hawari 11 160 122 453 39 232 993 317 2200 3896 8.02
Bu-hadi 12 88 112 190 3.1 80 532 98 1147 2290 7.45
North Baninah 13 128 188 301 11.1 80 851 136 1624 3250 7.28
Sidi-Farag 14 88 84 102 2.2 80 340 96 800 1600 7.50

The permissible limit of TDS in the drinking water is 1000 mg/L (WHO, 1993). However, in this
study, the TDS values were varied between 800 – 16038 ppm, with an average of 5290.214 ppm.
Among the studied samples, 5 of them exceeded the permissible limit. Calcium and Magnesium
in the study area ranged between 88-1600 ppm and 37 – 1459 ppm. In the normal groundwater
systems, the principal origin of these ions is carbonate minerals and their dissolution and
depositional processes. Weathering of silicate minerals are also contributing towards the
enrichment of these minerals. Fairly less abundance of the carbonate minerals in the study area
indicate that the major origin of Ca and Mg is silicate weathering. Na and K concentrations were
varied between 102- 2323 ppm and 2.2 – 235ppm. Sodium in the groundwater is largely
controlled by the saline intrusions, evaporates and silicate minerals. However, Na and K in the
study area could be derived from the weathering of the hard rocks, especially silicate weathering.
A relative lower concentration of Ca than Na shows the effect of cations exchange between these
minerals. Bicarbonate was the dominant anion in the study area, with an average concentration of
247.714 ppm. Apart from the dissolution of carbonated the major origin of bicarbonates are the
sewage systems. However, there is no prescribed permissible limit of this ion. Bicarbonate was
present in all samples. Chloride ion is generally used in delineating the saline intrusions. The
peculiar characteristics is that this ion has high mobility and hardly undergone for sorption.
Sulfate in the study area varied between 58- 2544 ppm. The major origin of Sulfate is the
dissolution of Gypsum and anthropogenic activities. The Salinity of water increases from
continental side of Benghazi plain toward the Kwoeffiah area, (as we close to the Mediterranean

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1st National Conference on Marine and Groundwater Pollution
(1st NCMGP-2017)

Sea) from 846ppm to 16038ppm. The concentration of Cl in the groundwater was 319 – 8156
ppm. The chloride content has the lowest value in Sidi Mansower-well-1 (319 ppm), however the
―Blue Lagoon‖, has the highest level with 8156ppm. The concentration of chloride content goes
up as we go to the northwest. Together, the salinity and chloride content are good evidence of the
hydraulic relationship between the microfissured – microporous limestone media and microkarst
system. The variance of rather high salinity near the Kwoeffiah area (Eocene and Miocene
aquifers) have to be explained by the effect of sea water intrusion as a result of over pumping
wells, especially at the coastal stretch. Electrical conductivity (EC) that has been measured in
different area shows different EC increase from the inside (south) to the North, from 1489
to28800 µS/cm, which mean all of these waters are brackish to salty water. Corresponding to
Jabbah cave, the chloride content and the EC considerable less than Habibi and Bohmira, which
mean, these areas have salty water. Corresponding to Al Mjdoub and Mrici, the samples show
more or less fresh water. The ionic value and pH of our samples are another indication of the
variety of water, as well as the percent of HCO3.
Another indication of the source of water could be figured out from the relationship between the
molar Na/Na+Cl and Ca/Ca+SO4. The ratios of this relationship are imperative to relate the
genetic originally. The water samples of the study area show that some samples are typically
from seawater, while the rest samples are to domain of evaporation (Fig. 2).

Scatter plot(Ca/Ca+SO4 vs Na/Na+Cl)

0.7 North Baninah

0.65

0.6 Habibi-2016

0.55
Ca/Ca+SO4

Jabbah
Sidi Mansower well-2
0.5 Majdob-2016
Sidi-Farag Sidi Mansower well-1
Bu-hadi
0.45 Buhmira-2016

Evaporation
0.4
Blue Lagoon
Sea water Ayn Zayanah
0.35 Koeiffyah-well
Ayn Zayanah spring Hawari

0.3
0.1 0.15 0.2 0.25 0.3 0.35
Na/Na+Cl

Fig. 2: Molar Na/Na+Cl and Ca/Ca+SO4 to differentiate water of different origin

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1st National Conference on Marine and Groundwater Pollution
(1st NCMGP-2017)

Water types
Piper diagram were made in such a way that the mill equivalents percentages of the major cations
and anions are plotted in separate triangle. These plotted points in the triangular fields are
projected further into the central diamond field, which provides the overall character of the water.
In contrast, in Chadha´s diagram, the difference in mill equivalent percentage between alkaline
earths (calcium plus magnesium) and alkali metals (sodium plus potassium), expressed as
percentage reacting values, is plotted on the X axis, and the difference in mill equivalent
percentage between weak acidic anions (carbonate plus bicarbonate) and strong acidic anions
(chloride plus sulfate) is plotted on the Y axis. The resulting field of study is a square or
rectangle, depending upon the size of the scales chosen for X and Y co-ordinates. The mill
equivalent percentage differences between alkaline earths and alkali metals, and between weak
acidic anions and strong acidic anions, would plot in one of the four possible sub-fields. The
major advantage of this diagram is that it can be drawn in any spreadsheet software packages.
Groundwater types were used by many researchers in their studies to understand the controlling
factors of the water chemistry (Aris et al. 2009; Martos et al. 2002; Mondal 2010; Rajesh et al.
2011; Ramesh and Elango 2011). In the present study along with groundwater chemistry, water
types were assessed using Piper diagrams. A Piper diagram (Fig. 4) was created for the selected
area using the analytical data obtained from the hydrochemical analysis. In general, we can
classify the sample points in the piper diagram into 4 fields. They are 1. Ca-Mg-Cl-SiO4 type, 2.
Ca-Mg-HCO3 type 3. Na-K-Cl-SiO4 type, 4. Na-K-HCO3 type as shown in figure 4. It is clear
the old water samples that were collected during the 80‘s is type-3 water. However, in the present
study water types were confined to the first with some mixed water. Majority of the samples
(70%) are plotted in the Ca-Mg-Cl field. Less than 20 % of the samples showed Na-K type. Rest
of them was fall in the mixed types. Evaluation of the water types using piper plot suggests that
there is a clear indication of the contribution from the weathering of the surrounding rocks.
Dominance of Ca and Mg in the groundwater samples collected from the Sidi Mansuwer wells
(1& 2) and Ayn Zayanh suggested an inverse ion exchange process. During this process Ca from
the Aquifer matrix will be exchanged by Na from the groundwater. However, in the other region
water is dominated by the mixed water. which is represented by the discharge zone.

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1st National Conference on Marine and Groundwater Pollution
(1st NCMGP-2017)

Fig. 4: Piper diagram showing the relative cation and anion compositions of the Benghazi Plane
water. This diagram confirms the Na-Cl type for Benghazi Plane water. The filled phosphoric
color of circles, square, triangle show the composition of 14 analyzed water samples in 2016.

Multivariate statistical analysis

Cluster analysis

Cluster analysis groups a system of variables into clusters on the basis of similarities (or
dissimilarities) such that each cluster represents a specific process in the system. Hierarchical
cluster analysis HCA is a powerful tool for analyzing water chemistry data, and formulating
geochemical models (Meng and Maynard, 2001). In this study, the (HCA) was applied to the raw
data for each of the different locations in Benghazi Plane, using XlStat (xcel Software). Several
similarity/dissimilarity measures are available from the XlStat package. A classification scheme
using the Euclidean distance for similarity measures and the Ward‘s method for linkage produces
the most distinctive classification where each member within a group is more similar to its fellow
members than to any member outside of the group (Gu¨ ler et al., 2002). Results from the HCA
for each location were reported in the form of dendrograms. On the basis of the connecting
distances between parameters and their positions on the dendrograms, distinctive clusters of the
variables were defined for each of the all locations along the Benghazi Plain. Though this
procedure is subjective, the distinction between clusters in this analysis is quite clear from the
dendrograms (Fig. 5).

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(1st NCMGP-2017)

0.984
0.986
0.988
0.99
Similarity

0.992
0.994
0.996
0.998
1
Sidi Mansower well-2

Sidi Mansower well-l

Ayn Zayanah spring

Majdob-2016
Jabbah

Habibi-2016
Sidi-Farag
Bu-hadi

N.Baninah

Blue Lagoon
Hawari

Buhmira-2016
Ayn Zayanah
Koeiffyah-well

Fig. (5) Hierarchical cluster analysis displaying four distinct groups

Four main groups are visible from the cluster analysis of data. Figure (5) presents the dendrogram
from the HCA. Group 1 comprises Koeiffyah-well, and Hawari, and represents the dissolution of
sulfide bearing rocks. This is an oxidation process which also affects the pH of the medium.
Group 2 is made up of Sidi Mansower-wells, and represents the weathering of albite and calcic
feldspar and the contribution of precipitation to water chemistry. Group 3 is made up of Buhmira-
2016, Majdob-2016, Habibi-2016, Ayn Zayanah, and the Blue Lagoon indicates that EC in the
water is more or less sea water. Group 4 is made up of Jabbah, Bu-hadi, North Baninah, and Sidi-
Farag they comprise TDS, EC, and HCO3.

Principal components and Factor analysis

PCA is far more commonly used than principal factor analysis (PFA). However, it is common to
use ‗‗factors‘‘ interchangeably with ‗‗components‘‘ in multivariate analysis. Factor analysis can
be performed on any kind of scientific data to establish a pattern of variation among variables or
reduce large data sets into factors for easy handling and interpretation. Factors are ranked in order
of merit. The first factor or component has the highest eigenvector sum and represents the most
important source of variation in the data (table 4). The last factor is the least important process
contributing to the chemical variation. Factor loadings on the factor loadings tables are
interpreted as correlation coefficients between the variables and the factors. In this study, PCA

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1st National Conference on Marine and Groundwater Pollution
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was applied to chemical data from the Benghazi plane to extract the principal factors
corresponding to the different sources of variation in the data. Here, PCA was selected for the
reasons stated above. In order to maximize the variation among the variables under each factor,
the factor axes were subsequently varimax rotated.

Table (4) Eigenvectors: for PCA of water chemistry in ppm

F1 F2 F3 F4 F5 F6 F7 F8 F9 F10
Ca 0.343 -0.017 -0.314 -0.204 -0.535 -0.069 0.276 -0.587 -0.121 -0.123
Mg 0.336 -0.130 -0.319 -0.239 0.792 0.044 -0.038 -0.273 -0.077 -0.009
Na 0.332 -0.152 0.451 0.600 0.164 -0.323 0.358 -0.163 -0.131 -0.019
K 0.345 0.028 0.064 -0.417 -0.011 -0.001 0.601 0.563 0.064 0.137
HCO3 0.174 0.689 0.543 -0.323 0.071 -0.029 -0.184 -0.233 -0.018 -0.034
Cl 0.343 -0.124 -0.033 -0.078 -0.126 -0.324 -0.448 0.376 -0.448 -0.443
SiO4 0.342 -0.114 0.174 0.175 -0.096 0.872 -0.090 0.039 -0.154 -0.078
TDS 0.345 -0.107 0.015 0.057 -0.059 -0.067 -0.205 0.025 0.857 -0.286
EC(µSec/cm) 0.344 -0.113 -0.013 0.021 -0.160 -0.134 -0.381 0.012 0.009 0.824
PH 0.194 0.657 -0.515 0.471 0.029 0.019 0.051 0.198 -0.002 0.019

Five principal components (PC) were extracted and rotated using the variable normalization
(Kaiser, 1960). An initial run using the Kaiser criterion (Kaiser, 1960) resulted in five principal
components. Moreover, it was observed that the fifth factor could be constitute a unique source of
variance in the hydrochemistry since it had only one loading greater than 0.10. It was therefore
dropped and four factors were chosen for variable rotation. The results (Table 6) show that the
four PC account for more than 90% percent of the variance, which is quite good and can be relied
upon to identify the main sources of variation in the hydrochemistry. PC1 has high loadings (0.5
– 0.993|) for pH, EC, K+, HCO3, SiO4 and Mg, Na, K, and Cl and accounts for 90% of the total
variance in the hydrochemistry in the area. Potassium and HCO3 both show positive loadings
under PC2 and are derived from the weathering of K-feldspars from the underlying geology, a
process which is accompanied by a rise in pH which accounts for <0.1% of the total variance,
contains high loadings for EC, Na+, HCO3, and could be represents the contribution of
agricultural activities and organic matter. PC3,4, and 5 have high loadings for EC, Ca2+, TS and
SO4, representing < ~ 0.1% of the total variance in the hydrochemistry at this location. they
represent the weathering of gypsum from the underlying sedimentary material. the total variance
in the hydrochemistry, shows high loadings for pH, Mg2+ and Cl. PC4 represents the
contribution of domestic wastes, which contain Mg-Cl. An interesting observation can be made
while comparing the loadings of PC2 to PC5.

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Table (6) Factor loadings of water chemistry

F1 F2 F3 F4 F5
Ca 0.985 -0.020 -0.125 -0.048 -0.098
Mg 0.967 -0.157 -0.127 -0.056 0.145
Na 0.955 -0.184 0.180 0.140 0.030
K 0.993 0.034 0.026 -0.097 -0.002
HCO3 0.500 0.835 0.217 -0.075 0.013
Cl 0.987 -0.150 -0.013 -0.018 -0.023
Sio4 0.983 -0.138 0.070 0.041 -0.018
TDS 0.991 -0.130 0.006 0.013 -0.011
EC(µSec/cm) 0.990 -0.137 -0.005 0.005 -0.029
PH 0.558 0.796 -0.206 0.110 0.005
It is seen that loadings of PCs have low magnitudes for the same variables. Also, the correlation
analysis of the principal component loadings has revealed that the highest correlation (~ 0.99)
exists between TDS and Cl.

Table (7) Correlation matrix of water chemistry

Variables Ca Mg Na K HCO3 Cl Sio4 TDS EC(µSec/cm) PH

Ca 1 0.960 0.913 0.978 0.451 0.979 0.961 0.978 0.980 0.553
Mg 0.960 1 0.925 0.956 0.331 0.977 0.959 0.976 0.974 0.435
Na 0.913 0.925 1 0.933 0.353 0.964 0.978 0.973 0.969 0.365
K 0.978 0.956 0.933 1 0.536 0.975 0.969 0.978 0.976 0.566
HCO3 0.451 0.331 0.353 0.536 1 0.366 0.387 0.388 0.379 0.891
Cl 0.979 0.977 0.964 0.975 0.366 1 0.987 0.998 0.999 0.432
Sio4 0.961 0.959 0.978 0.969 0.387 0.987 1 0.993 0.991 0.429
TDS 0.978 0.976 0.973 0.978 0.388 0.998 0.993 1 1.000 0.450
EC(µSec/cm) 0.980 0.974 0.969 0.976 0.379 0.999 0.991 1.000 1 0.445
PH 0.553 0.435 0.365 0.566 0.891 0.432 0.429 0.450 0.445 1

The next highest correlation existing between Ca and Cl has a magnitude equal to 0.97.
Hence it is seen that the correlation between SiO4 and Cl is significantly higher than the others
(Table 7). Thus, a biplot of PC1 against PC5 was prepared (Fig. 6).

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2
Sidi Mansower- Jabbah Buhmira-2016
well-1 Koeiffyah-well
1 Sidi Mansower-
Majdob-2016
well-2 Habibi-2016
0
Hawari Blue Lagoon
Ayn Zayanah
-1 Ayn Zayanah
Sidi-Farag spring
Bu-hadi
-2 North Baninah

-3
-3 -2 -1 0 1 2 3 4 5 6

Fig. (00) Biplot of the PC of the water samples

The presence of multiple variables in the same quadrant suggests close association
between them. The association between pH and HCO3 is understandable as their equilibrium
values are controlled by oxidation–reduction processes. The change in salinity is associated with
distance from the costal due to the freshwater inflow. Scanning the plot, one can see that among
the K and Ca lie in different quadrants, and thus they are separated. It can thus be concluded that
the sources for contamination. In Fig. ??, two clusters of points are seen; one in the first quadrant
where pH and HCO3 lie and another in the fourth quadrant, where the rest of the variables. It may
could because some sample have been collected from the environment.

Conclusions
The application of both the HCA and PCA with different rotation, however, has been
more effective than the use of either one of them alone. The hydrochemistry of the basin is
controlled largely by the weathering of minerals (silicates, carbonates, and gypsum) from the
underlying meta-sediments of the decay of organic matter from the heavily unclean regions.
There is strong evidence of high anthropogenic impacts on the hydrochemistry of the basin,
though there are variations at the different locations studied. The hydrochemistry at Benghazi
region is principally controlled by the weathering of silicate minerals, whereas those of in land
are, respectively, influenced by precipitation and domestic wastewaters, and the decay of organic
matter.

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1st National Conference on Marine and Groundwater Pollution
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1st National Conference on Marine and Groundwater Pollution
(1st NCMGP-2017)

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