DOI: https://dx.doi.org/10.4314/gjgs.v20i1.

GLOBAL JOURNAL OF GEOLOGICAL SCIENCES VOL. 20, 2022: 25-40

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HYDROCHEMICAL CHARACTERIZATION AND EVALUATION OF
GROUNDWATER QUALITY OF ZAMFARA AREA, NORTHWEST,
NIGERIA
SHUAIBU A. M., GARBA M. L AND ABUBAKAR I. Y.

(Received 26 November 2021; Revision Accepted 28 January 2022)

ABSTRACT

This study deals with hydrochemical assessment of groundwater within the lithological framework underlain Zamfara
State, Northwestern Nigeria with the aim of ascertaining its suitability for human consumption. Groundwater samples
were collected from boreholes tapping the aquifer of the area and analyzed for various physico-chemical parameters,
+ + 2+ 2+ -
such as total dissolve solids, electrical conductivity (Ec), pH, temperature, Na , K , Ca , Mg , HCO3, Cl , SO4, NO3,
PO4, and trace elements (Mn, Cu, Zn, Fe, Pb and Cr). The results obtained were subjected to multivariate statistical
analysis, water quality index method, and hydrochemical variation plots for proper characterization. As far as suitability
is concerned most of the studied physic-chemical parameters trace elements (iron, lead and chromium ions) revealed
average concentrations lower than the permissible limit set for domestic water use by World Health Organization.
However, the compiled overall water quality index for the studied groundwater shows „very poor water quality‟. Due to
the fact that WQI rating reflect the composite influence of different water quality parameters. The result of the
multivariate statistical analysis, as applied to the chemical data set of the studied groundwater provides an insight into
the underlying controlling hydrochemical processes in the area. Four factors including factor-1 (total hardness,
chloride, nitrate, manganese, bicarbonate and alkalinity), factor-2 (TDS, conductivity, total hardness, magnesium and
calcium), factor-3 (Temperature, sodium, potassium, copper, zinc, iron and chromium), factor-4 (calcium, magnesium
and nitrate) represents the signatures from dissolution of bedrock through which the groundwater passes, ionic
mixing, leaching from the lateritic overburden, agricultural activities (fertilizer application) and effluent from waste
dumpsites in the study area. The distribution of major ions in the groundwater shows relative abundance of cations:
+ + 2+ 2+ - - 2-
Na +K > Ca > Mg ; while the relative abundance of the anions is: Cl > HCO3 > SO4 . Groundwater in the aquifer
of the study area are majorly of evolved type with mixing of ionic concentrations. Alkali‟s are more in abundant to that
of alkaline earth, while Cl and HCO3 dominate SO4 and NO3 concentration. The water samples are basically „Alkali
- -
waters‟ with „Earth Alkaline‟ components that are predominantly HCO 3 and Cl .The relative abundance of the three (3)
dominant water types are as thus: Na-HCO3-Cl > Ca-Mg-HCO3-Cl > Na-Ca-Cl. Simple mineral dissolution or mixing
processes is mainly responsible for the variation in the hydrochemistry of the groundwater of the study area.

KEYWORDS: Hydrochemical classification, Water quality index, Multivariate statistical analysis, Groundwater,
Zamfara State.

1.0 INTRODUCTION The character of groundwater in different aquifers over

space and time proved to be an important technique in
Groundwater contains minerals carried in solution, the solving different geochemical problems
type and concentration of which depends upon several (Srinivasamoorthy et al., 2005).
factors like soluble products of rock weathering and The importance of groundwater as an alternative water
decomposition in addition to external polluting agencies supply is increasingly recognized, in response to
and changes in space and time. As a result of chemical escalating decreasing quality of surface waters and low
and biochemical interaction between groundwater and supply from various water vendors. It is often thought to
contaminants from urban, industrial and agricultural be cleaner and easier to treat as compared to surface
activities along with geological materials through which it water and as a result, many wells have either been sunk
flows, it contains a wide variety of dissolved inorganic or drilled (Rosenberry, 2003, Arabi et al., 2012).
chemical constituents in various concentrations. Possible water quality issues and decreasing water
Shuaibu A. M., Geology Department Federal University Gusau, Zamfara, Nigeria
Garba M. L., Geology Department Ahmadu Bello University Zaria, Nigeria
Abubakar I. Y., Geology Department Ahmadu Bello University Zaria, Nigeria

© 2021 Bachudo Science co. Ltd. This work is licensed Under Creative Commons Attribution 4.0 international license.
26 SHUAIBU A. M., GARBA M. L AND ABUBAKAR I. Y.
levels increase the need for a comprehensive and also support domestic and industrial water supply.
understanding of the groundwater system that would Due to rise in agriculture production and demographic
yield better management of the resources. change, groundwater has set a declining trend
Clean, safe and adequate freshwater is of utmost throughout the major aquifer of the study area. The
importance to human existence and survival of living current rate of groundwater abstraction so far has
components in the ecosystem. Water quality issues are exceeded the rate of groundwater recharge. As pumping
complex and diverse, deserving urgent global attention wells tapping the various aquifers of the region are
and action (Ige et al., 2008). The decline in water quality unevenly distributed, the consequences of this
has become a global issues of concern because of its unbalanced groundwater exploitation vary from one part
inherent ability to hydrological cycle. The past decade of the study area to another (Garba and Schoeneich,
has been remarkable impact of man on the environment 2005). The baseline problems from too little water and
due to unprecedented increase in population and rapid contamination noticed by this research in the entire
rate of urbanization as well as the intensification and Zamfara State call for proper assessment and
expansion in agricultural practices. This has led to management of the available groundwater resources.
progressive and continued degradation of groundwater Therefore, there is a need for a thorough assessment of
resources. Contamination of groundwater is an the quality of water available for human, agricultural and
important vehicle for spread of diseases (Ezeigbo, 1989; industrial purposes. Moreover, water resources
Abubakar et al., 2017). safeguard policy requires periodic assessment of both
More so, the need for water has resulted in an groundwater quantity and quality. The present study
increasing withdrawal of groundwater in sensitive areas focuses on assessment of groundwater quality and its
like crystalline environments, where aquifers may suffer suitability for domestic purpose for the proper
from over abstraction, which consequently may result in management.
deterioration of its quality (Akujieze et al., 2007, Amadi
and Olasehinde, 2008, Amadi, 2010, Kanade and 1.1 STUDY AREA
Gaikwad, 2011, Akano, 2015, Shuaibu and Abdullahi, This research covers the entire Zamfara State with total
2
2015, Abubakar et al., 2017). area coverage of 39,762Km , within the North Western
0
It is worthy to note that water quality has been evaluated Nigeria (Figure 1), with Longitude: 5 1ʹ27.638˝E to
0
in the last years owing to greater understanding of 13 10ʹ45.537˝N, and Latitude: 6˚18ʹ13.709˝E to
mineralization process and greater concern about its 11˚49ʹ4.152˝N. Temperatures are generally extreme,
origin (Shane and Jerzy, 2003). Water quality shows with average daily minimum of 18°C, during cool months
water-rock interaction and indicates residence time and of December and January while in the hottest months of
recharge zone confirmation (Sanchez and Trenolieres, April to June, an average maximum of 38°C and
2003; Cronin et al., 2005). Thus, water quality indicators minimum of 24°C temperatures are recorded (NiMET,
must reflect mineralization process, integrate reservoir 2020).
properties and groundwater recharge rate and flow Rainfall is generally low; the average annual rainfall
direction (Adams et al., 2001; Legout, 2005; Andre et al., ranges from 600 to 1000mm across the entire State.
2005; Grassi and Cortecci, 2005). Much of the rain, falls between the months of May to
Consequently, water is a scarce resource in Zamfara September, while the months of October to April
State due to the climate and the nature of the dominant experienced little or no rainfall. Evaporation is high,
geologic framework as well as anthropogenic influences. ranging from 80mm in July to 210mm in April to May
Especially during dry season when the yields of open (NiMET, 2020). A monthly average evapo-transpiration
wells and boreholes falls and surface water from rivers, range of about 140mm represent 30 of monthly average
stream, and impounding reservoirs become dry. precipitation into the catchment.
Groundwater is the major source of water for irrigation

The study area belongs to the Sudan savannah region of Africa; an area most affected by droughts (Figure 1).
HYDROCHEMICAL CHARACTERIZATION AND EVALUATION OF GROUNDWATER QUALITY 27

Figure 1: Map of the Study Area

2.0 GEOLOGICAL SETTING origin (Figure 2). Its maximum thickness is reported to
About 90% of the State is underlain by a variety of be up to 300m, near the Niger border. The base is
crystalline rocks of the basement complex of north marked by conglomeratic beds which are well preserved
western Nigeria described by McCurry (1976) to be and exposed by the road side at Tureta and Ruwan
composed largely of gneiss, schist, migmatite, granite Kalgo (Kogbe, 1976). These basal beds contain rounded
and granodiorite (Figure 2). The structural features quartz cobbles and pebbles and attain a thickness of
commonly exhibited by the basement rocks include about 3m. The formation is the oldest sedimentary rocks
foliation, lineation, folds, rock-rock contacts, faults and in the Northern parts of the Sokoto basin, it lies
joints. The rest of the state is underlain by the oldest uncomfortably on the Basement Complex. The
sediments of the Sokoto (Illullemeden) basin described indication, from borehole sections, is that the basal
by Oteze (1976) and Kogbe (1976). Groundwater in the conglomerates are overlain by beds which are more
basement rocks of the study area are mainly sourced argillaceous from the bottom to the top (Ogilbee et al.,
from fractures and joints (Yaya et al, 2001) and in the 1965). The intergrannular pores of fine to coarse (white
About 10% of the study area is underlain by Gundumi or light grey) sand or gravel in Gundumi formation
formation which consists of clays, sandstones and served as its aquiferous layer (Oteze, 1976).
pebble beds, thought to be lacustrine and fluviatile in
28 SHUAIBU A. M., GARBA M. L AND ABUBAKAR I. Y.

Figure 2: General Geological Map of Zamfara State, (Nigeria Geological Survey Agency, 2006).

3.0 MATERIAL AND METHODS Multivariate Statistical Analysis: The data obtained from
In this study, one hundred (100) groundwater samples laboratory analyses were used as variable inputs for
were collected from boreholes, covering entire study factor analyses (R-Mode). A factor analysis was
area of Zamfara State, Northwestern Nigeria (Fig. 1), performed using the SPSS package described by Nie et
and the water samples were analyzed for major, minor al. (1975). Before the analysis, the data were
and trace elements. standardized to produce a normal distribution of all
variables (Davis, 1973). This was followed by a
3.1 SAMPLING TECHNIQUES preparation of a correlation matrix of the data from which
The samples were collected during the peak of rainy initial factor solutions were extracted using the principal
season (August, 2018). During the exercise, global component analysis method. Factor extraction was done
positioning system was used to obtain the coordinates, with a minimum acceptable eigenvalue of 1 (Kaiser,
one litre of plastic rubbers was used to collect the 1958; Harman, 1960). Orthogonal rotation of these initial
samples. The plastic rubbers were washed, dried and factors to terminal factor solutions (Table 1) was done
rinsed with the water before filling it to capacity and with Kaiser‟s varimax scheme (Kaiser, 1958). This
labelled accordingly. Prior to collection of water method maximizes the variance of the loadings on the
samples, the physical parameters were determined in factors and hence adjusts them to be either +1, -1 or
the field using portable standard equipment (pH meter: zero (Davis, 1973). Factor score coefficients are derived
PHS 125 REX, Conductivity meter: PCE-SM11). from factor loading. Factor scores are computed for
After the sample collection, the samples were stored in a each sample by a matrix multiplication of the factor
cool box and later transported to the Water Quality score coefficient with the standardized data. The value
Laboratory, Federal University of Technology, Minna. of each factor score represents the importance of a
The Atomic Absorption Spectrophotometer (AAS) was given factor at the sample site. It should be noted that a
2+
used for the determination of the concentrations of Ca factor score > +1 indicates intense influence by the
2+ 2+ 2+ 2+
and Mg as well as the trace metal; Pb , Cu , Cr , process. Highly Negative values (< -1) reflects areas
2+ 2+ 2+
Mn , Zn and Fe while flame analysis was used for virtually unaffected by the process while zero score
+ +
the determination of the concentration of Na and K . shows areas with only moderate effect of the process.
2-
The colorimetric method was used to determine SO 4 The four factor scores represent the four types of
and PO4. The Ultra-Violet Spectrophotometer (UVS) elemental enrichment (Table 2).
-
was utilized in the determination of NO3 while the WQI: Water Quality Index: Water quality index (WQI) is
-
concentration of HCO3 and CO2 were determined using one of the most effective tools to communicate
titrimetric method. information on the quality of water to the concerned
The obtained chemical data set were subjected to water citizens and policy makers. It thus, becomes an
quality index analysis, multivariate statistical important parameter for the assessment and
interpretation and hydrogeochemical graphical models management of surface water and groundwater. WQI is
for optimal characterization of the hydrogeochemical a scale used to estimate an overall quality of water
processes. based on the values of the water quality parameters
HYDROCHEMICAL CHARACTERIZATION AND EVALUATION OF GROUNDWATER QUALITY 29
(Amadi, 2011). It is a rating reflecting the composite A quality rating scale (qi) for each parameter is
influence of different water quality parameters. WQI is assigned by dividing its concentration (C i) in each water
calculated from the point view of the suitability of sample by its respective standard (Si) and the result
groundwater for human consumption (Lambarkis et al., multiplied by 100. Relative weight (W i) was calculated by
2004, Amadi, 2010). a value inversely proportional to the recommended
Calculation of WQI: The Water Quality Index (WQI) was standard (Si) of the corresponding parameter:
calculated using the Weighted Arithmetic Index method. Wi = 1/Si
The quality rating scale for each parameter qi was (2)
calculated by using this expression: The overall Water Quality Index (WQI) was calculated
qi = (Ci / Si ) x 100 by aggregating the quality rating (Qi) with unit weight
(1) (Wi) linearly.

Where: qi: the quality of the ith parameter, wi: the unit weight of the ith parameter and n: the number of the parameter
considered. Generally, WQI were discussed for a specific and in-tended use of water. In this study the WQI for
drinking purposes is considered and permissible WQI for the drinking water is taken as 100.
All the physical and chemical parameters analyzed from the studied sampled water were used to calculate the WQI in
accordance with the required procedures and the results contained in the table 5, subsequently this equation was
∑
applied [ ∑
] to the entire water quality classification scheme.

4.0 RESULTS AND DISCUSSION

The descriptive statistical summary of the hydrochemical results is presented in Table 1.

Table 1: Statistical summary of the physical and chemical analyses of Groundwater samples

Parameters Minimum Maximum Mean Std. Deviation Skewness WHO (2017)

Temperature 27 33 30.16 1.19 -0.24 Ambient
pH 5.7 8.8 6.78 0.57 0.83 6.5 - 8.5
TDS 67.2 967.04 470.58 227.28 0.21 1000
Ec 105 1688 753.20 374.69 0.32 1500
Alkalinity 52 498 190.22 97.94 1.11 200
TH 17 296 99.34 68.90 1.03 200
Cl 6.6 234 68.36 52.67 1.34 250
HCO3 0 429 82.17 75.37 2.17 600
SO4 0 184.3 83.96 56.71 -0.07 250
PO4 0.01 0.8 0.12 0.08 6.15 5
CO2 1.14 131 10.37 13.32 7.71
NO3 0 99 3.07 12.29 6.28 50
Na 4.55 900 87.68 144.12 2.96 200
K 0.54 86 11.77 15.67 2.81 100
Mg 0.49 73.96 19.24 17.44 1.55 150
Ca 3.63 159.56 48.05 32.49 1.17 200
Mn 0 2.35 0.05 0.24 9.59 0.2
Cu 0 0.42 0.08 0.12 1.22 2
Zn 0.01 0.72 0.19 0.12 0.84 5
Fe 0 7.89 0.28 0.83 8.17 0.3
Pb 0 0.53 0.05 0.13 2.53 0.01
Cr 0 0.81 0.05 0.12 4.12 0.003

The pH values range between 5.7 to 8.8 with mean to 7.5 as recommended by WHO, (2017). Most often
0
value of 6.78 while water temperature varies from 27 C biochemical processes in groundwater are influenced by
0 o
to 33 C with mean value of 30.16 C (Table 1). They are changes in pH and temperature, as chemical
important water quality indicator and plays important role substances dissolve more readily in water under low pH
in the dissolution of chemical substances in water. The and high temperature conditions.
mean value of pH falls within the acceptable limit of 6.50
30 SHUAIBU A. M., GARBA M. L AND ABUBAKAR I. Y.
Total dissolve solids (TDS) indicate the amount of concentration of Ca and Mg ions is believed to be
substance dissolved in water. Its concentration in the responsible for the hardness of the studied groundwater.
studied water samples range between 67.2 to 967.04 The mean concentrations of anions in the studied water
mg/l with average value of 470.88mg/l. This value samples (chloride, sulphate, bicarbonate, nitrate, and
revealed that the groundwater is fresh. However, value phosphate) is lower than their maximum recommended
of electrical conductivity (EC) varied between 105 to limit for domestic water use (WHO, 2017). Similarly, the
1688 µs/cm with mean value of 753.2 µs/cm (Table 1) average concentration of the major cations (Ca, Mg, Na
as against their respective maximum permissible limit of and K) were equally below their respective
1000mg/l and 1500 µs/cm respectively. This is an recommended permissible limit (WHO, 2017, table 1).
+
indication of moderate ionic dissolution in studied Nonetheless, result of Na shows maximum
groundwater. The large variation in EC values is concentrations of 900 mg/L which is above the threshold
attributed to geochemical evolution of groundwater of WHO, (2017) standard for drinking water. This
through rock-water interaction and possible suggest decomposition of feldspathic minerals in a
anthropogenic influences. location of the particular sample.
+2
The concentration of alkalinity of the studied water However, Fe concentration range between 0 to 7.89
samples range between 52 to 498 mg/l with an average mg/L with mean value of 0.28 mg/L against its
value of 190.22 mg/l. Its permissible limit is 200mg/l permissible limit of 0.3 mg/L by WHO, (2017). This
(WHO, 2017). This imply moderate dissolution of shows that some locations within the area of study have
mineral substance from lithologic framework. Total elevated iron concentration which is majorly sourced
hardness concentration varied between 17 and 296 mg/l from superficial material (clay mineral) as shown in
with mean value of 99.34 mg/l (Table 1). The elevated figure 3.

+2
Figure 3: Plot of Fe in the studied water samples against its WHO permissible limit
+2
Concentration of lead (Pb ) in the water samples shows mean value that is higher to its permissible standard limit for
drinking water, however, many locations depict concentration below the WHO, (2017) standard limit for drinking
water as shown in figure 4.
HYDROCHEMICAL CHARACTERIZATION AND EVALUATION OF GROUNDWATER QUALITY 31

+2
Figure 4: Plot of Pb in the studied water samples against its WHO permissible limit
Furthermore, the concentration of chromium ion in groundwater samples range between 0 and 0.81 with mean value
of 0.05 which is above its permissible limit for drinking purposes (WHO, 2017, table 1), nonetheless, many localities
shows concentration of chromium ion below the threshold of WHO, (2017) (Figure 5).

+2
Figure 5: Plot of Cr in the studied water samples against its WHO permissible limit
Naturally, trace elements occur in varying quantities in rocks depending on the geochemical composition of the
geological formation. As a result of the mobility of these elements in soil, they flow from the surface to the water-
bearing formation below. Also, these elements can also result from anthropogenic sources such as improper waste
disposal and the application of insecticides. The low concentration noticed in majority of water samples (95%)
collected from the study area could be as a result of the depth to the aquifer, which prevented the water-bearing
formation from every form of an external pollutant that could influence the purity of the groundwater.
32 SHUAIBU A. M., GARBA M. L AND ABUBAKAR I. Y.
4.1 MULTIVARIATE STATISTICAL ANALYSIS OF HYDROCHEMICAL COMPONENTS

Results of the factor analysis (R-Mode) of the groundwater chemistry data (n=100) indicates four factors (Table 2).

Table 2: Varimax rotated factor loading matrix for groundwater chemistry

Parameters Factor 1 Factor 2 Factor 3 Factor 4 Communalities

Temperature_°C 0.452 -0.236 0.513 0.074 0.528
pH -0.144 -0.118 -0.466 0.261 0.32
Total Dissolve
-0.238 0.682 -0.407 -0.349 0.809
Solids
Conductivity µs/cm -0.254 0.698 -0.352 -0.342 0.793
Total Hardness 0.539 0.522 0.274 -0.275 0.714
Alkalinity 0.733 0.308 0.211 -0.222 0.725
Clˉ 0.784 0.169 0.133 -0.252 0.725
HCO₃ 0.737 0.35 0.152 -0.201 0.729
SO₄ -0.267 -0.042 -0.408 -0.589 0.587
PO₄ -0.223 0.249 -0.706 0.127 0.626
CO₂ 0.342 0.191 0.395 -0.286 0.391
NO₃ 0.669 0.395 -0.05 0.446 0.805
Na⁺ -0.642 0.453 0.345 0.065 0.74
K⁺ -0.5 0.138 0.336 0.316 0.482
Mg² 0.388 0.502 -0.282 0.491 0.722
Ca²⁺ 0.104 0.72 -0.133 0.503 0.8
Mn² 0.562 0.419 0.115 0.156 0.529
Cu² -0.775 0.377 0.369 0.022 0.879
Zn² -0.528 0.3 0.322 0.017 0.472
Fe² 0.019 -0.259 0.305 0.21 0.205
Pb² -0.715 0.424 0.379 -0.091 0.844
Cr² -0.607 0.231 0.333 0.019 0.533
Eigen Value 5.916 3.499 2.682 1.86
Cum. Eigen 5.916 9.415 12.097 13.957
% Variance 26.892 15.906 12.192 8.455
Cum. Variance 26.892 42.798 54.989 63.44
Extraction Method: Principal Component Analysis.

Factor 1: account for 26.89% total data variance as groundwater movement or anthropogenic means via
shown in table 2 and presents significant and positive leachate migration from soak away, pit-latrine,
loading of total hardness, chloride, nitrate, manganese, dumpsites and industrial wastes. It equally revealed
bicarbonate, and alkalinity (Table 2). This factor is the much of ionic mixing as a major process of the
most significant factor because it explain more than one groundwater evolution against ionic exchange.
third of the total variance. It has been demonstrated by Consequently, this result revealed that calcium and
high positive loading (0.733, 0.784 and 0.737) for magnesium ions are essential contributor to the
alkalinity, chloride and bicarbonate ions. Natural water hardness of groundwater in the study area.
alkalinity is determined by the soil and bedrock through Factor 3: account for 12.19% total variance explain
which it passes, which could contain carbonate, (Table 2) with significant loading of temperature,
bicarbonate, and hydroxide compound including silicate sodium, potassium, copper, zinc, iron and chromium
+ +
minerals. The high positive factor loading of bicarbonate ions (Table 2). The positive loading of Na and K
and alkalinity suggest rainwater as the major source of suggest dissolution of silicate minerals (weathering of
recharge of the aquifer. And lithological framework as feldspathic minerals) into the groundwater body, most
the source of groundwater chemical enrichment. The especially during the wet season of the year. The
total hardness show positive loading which signifies positive loading of heavy metals could either be both of
moderate to high mineralization of the groundwater natural or anthropogenic (discharge from mining and
within the study and this could be from the dissolution of agricultural activities).
silicate minerals from crystalline basement rock units High temperature in the study area encourages rapid
that underlain approximately 80% of the study area. chemical weathering, which leads to the formation of
Consequently, chloride and nitrate positive loading lateritic soils in the area. They are characterized by the
signify groundwater enrichment from anthropogenic presence of iron and aluminum oxides or hydroxides,
sources through leachate flow from agricultural activities particularly those of iron, which give the reddish-brown
(use of inorganic fertilizers and dumpsites). or yellow colour to the soil. The iron in groundwater is
Factor 2: reveal 15.91% of the total variance explain leached from thick lateritic overburden in the area
(Table 2) with high positive loading of total dissolve through the porous and permeable formation into the
solid, electrical conductivity, total hardness, magnesium shallow water table below it. Leachate of metallic object
and calcium concentrations. The TDS and the from dumpsites also migrates through the unconfined
conductivity are as a result of the dissolution of ions in highly permeable sandy formation to the water table.
the water through natural means in the course of Iron may also be present in drinking water as a result of
HYDROCHEMICAL CHARACTERIZATION AND EVALUATION OF GROUNDWATER QUALITY 33
the use of iron coagulants or the corrosion of steel and 4.2 CORRELATION MATRIX FOR HYDROCHEMICAL
cast iron pipes during water distribution as well as COMPONENTS
weathering process of minerals. Iron is one of the most Table 3 shows the results of correlation analysis of
abundant metals in the earth‟s crust and an essential major, minor and trace elements. The data illustrate that
2+ 2+
element in human nutrition. Estimates of minimum daily major ions (Mg , Ca ) with TDS, EC, total hardness
requirement for iron depend on age, sex, physiological and alkalinity are significantly correlated. This suggest
status and iron bioavailability. Excessive iron in the body similar source of enrichment which is mostly natural
+2
does not present any health hazard, only the turbidity, dissolution of rock forming minerals. However, Mg and
+2
taste and appearance of the drinking water will usually Ca show significant correlation with pH, nitrate and
be affected. chloride ions of the groundwater of the study area, thus
Positive loading of heavy metals such as copper, zinc, suggesting chemical weathering of the bedrock (source
and chromium ions suggest dissolution of a mineralized of mineral enrichment) and rainfall as the major source
ore body hosted by younger metasediments rock units. of the groundwater recharge (Table 3). However, the
Factor 4: account for 8.46 % of the total variance (Table positive correlation of nitrate against manganese and
2) with high positive loading of calcium, magnesium and calcium indicated enrichment from anthropogenic
nitrate (Table 2). This affirmed the divergent source of sources
the studied groundwater as being from both geogenic Alkaline ions show broad affinity with trace elements in
(dissolution of mineral matter from underlain lithologic the studied groundwater samples as they depict positive
units) and the anthropogenic source (leachate flow from correlation with Na, K, Mg, and Ca. This indicate an
inorganic fertilizer as well as indiscriminate waste dump enrichment from both natural and anthropogenic
across the study area). sources. It equally suggest anionic mixing during wet
season and majorly rock-water interactions. Though
positive correlation of total hardness and Nitrate ion
illustrate an impact ofs leachate flow from organic
matter.
 34 SHUAIBU A. M., GARBA M. L AND ABUBAKAR I. Y.

Parameter Temp pH TDS Ec Alkalinity TH Cl HCO3 SO4 PO4 CO2 NO3 Na K Mg Ca Mn Cu Zn Fe Pb Cr

Temp 1
pH .227* 1
TDS -0.138 0.167 1
Ec -0.128 0.172 .981** 1
Alkalinity -0.032 0.07 .446** .455** 1
TH -0.032 0.077 .312** .318** .573** 1
Cl 0.165 0.039 0.167 0.154 .218* .212* 1
HCO3 -0.019 0.141 -0.047 -0.054 0.163 0.178 -0.048 1
SO4 0.05 -0.08 .208* .232* -0.06 0.057 .206* -.460** 1
-
PO4 .258** -0.012 .275** .258** -0.069 -0.167 -0.019 -0.169 .245* 1
CO2 -0.011 -0.068 -0.029 -0.036 -0.086 -0.044 .212* 0.03 0.088 -0.027 1
-
NO3 -0.019 -0.092 -0.022 -0.015 .202* .295** .251* 0.038 0.056 -0.006 0.002 1
- - -
Na .271** .263** 0.043 0.065 -0.065 -0.109 -0.193 -0.175 .234* 0.104 0.065 0.015 1
K -0.104 0.069 0.033 0.053 -0.12 -0.167 -0.136 0.027 -0.027 0.013 0.02 -0.1 .383** 1
-
Mg .320** .266** .363** .372** .208* 0.055 .438** 0.011 0.183 0.016 0.023 -0.08 -.330** -0.087 1
-
Ca 0.15 0.15 .376** .393** .232* 0.187 .346** -0.1 .240* .249* 0.061 .294** 0.086 -0.058 .631** 1
Mn 0.07 -0.045 0.002 0.014 .290** .319** .267** 0.095 0.065 -0.069 0.017 .795** 0.029 -0.065 -0.039 0.19 1
- -
Cu .359** -0.195 0.156 0.186 -0.136 -0.144 -0.136 -.202* .221* 0.091 0.098 -0.17 .672** .347** -0.064 0.12 -0.11 1
Zn 0.022 0.147 0.067 0.112 -0.058 -0.059 -0.062 0.123 -0.114 -0.087 0 -.295** -0.048 0.093 .272** 0.09 -0.11 .265** 1
-
Fe 0.096 0.016 -0.115 -0.117 -0.053 -0.02 -0.077 -0.032 0.003 -0.152 0.001 0.172 0.116 .241* -0.154 -0.13 0.056 -0.068 -0.12 1
- -
Pb .267** -.251* 0.059 0.091 -0.062 -0.113 -0.196 -.221* .282** 0.077 0.062 -0.09 .860** .319** -.282** 0.05 -0.06 .762** 0.043 0.019 1
-
Cr -0.151 -0.135 0.014 0.043 -0.161 -0.17 -0.16 -.213* .210* 0.038 0.027 -0.1 .520** .398** -0.194 0 -0.06 .529** 0.052 0.033 .744** 1
* Correlation is significant at the 0.05 level (2-tailed).
** Correlation is significant at the 0.01 level (2-tailed).

10
HYDROCHEMICAL CHARACTERIZATION AND EVALUATION OF GROUNDWATER QUALITY 35
4.3 WATER QUALITY INDEX (WQI) OF THE STUDY AREA

The computed overall WQI value using equation (4) is 92.05 which is in the class of “very poor water quality” as
shown in table 5.

Table 4: Standard water quality classification scheme based on WQI value

Parameters C S q1 w1 q1w1
Temp 30.16 25 120.64 0.04 4.83
pH 6.78 7.5 90.39 0.13 12.05
TDS 470.58 500 94.12 0.002 0.18
Ec 753.20 1000 75.32 0.001 0.08
Alkalinity 190.22 200 95.11 0.005 0.48
TH 99.34 200 49.67 0.005 0.25
Cl 68.36 250 27.34 0.004 0.11
HCO3 82.17 100 82.17 0.01 0.82
SO4 83.96 100 83.96 0.01 0.84
PO4 0.12 5 2.39 0.2 0.48
NO3 3.07 50 6.15 0.02 0.12
Na 87.68 200 43.84 0.005 0.22
K 11.77 100 11.77 0.01 0.12
Mg 19.24 150 12.83 0.007 0.09
Ca 48.05 200 24.03 0.005 0.12
Mn 0.05 0.2 22.5 5 112.5
Cu 0.09 1 8.48 1 8.48
Zn 0.19 3 6.64 0.333 2.21
Fe 0.29 0.3 95.3 3.333 317.67
Pb 0.05 0.05 103.2 20 2064
Cr 0.05 0.05 104.4 20 2088

Table 5: Computed WQI values for the study area

WQI Value Rating of Water Quality Grading

0-25 Excellent water quality A
26-50 Good water quality B
51-75 Poor water quality C
76-100 Very Poor water quality D
Above 100 Unsuitable for drinking purpose E

4.4 HYDROCHEMICAL EVOLUTION OF THE expected as possible recharge from rainfall increase the
GROUNDWATER IN THE STUDY AREA amount of chemical weathering within the aquifer
The results of groundwater chemistry were analyzed to system, during the wet season.
decipher chemical alteration and to mask of natural or The Gibb‟s diagram highlights the supremacy of
meteoric characteristics of groundwater. Gibbs (1970) weathering of rocks in controlling the geochemistry of
plot was used to determine major processes controlling the water samples in the study area. It should be noted
the groundwater chemistry. The groundwater samples that no data point plotted above and below the
points on the Gibbs diagram suggest that the boomerang, where water composition is dominated by
groundwater chemistry is controlled principally by rock- evaporation-crystallization and atmospheric precipitation
water interaction (weathering) (Figure 6). This is respectively.
36 SHUAIBU A. M., GARBA M. L AND ABUBAKAR I. Y.

Gibb's plot of water samples

100000 Na + K/Na + K + Ca Cl/Cl + HCO3

Evaporation-
Crystallisation
10000 Dominance
TDS (mg/L)

1000

Rock-weathering
Dominance
100

10 Atmospheric
Precipitation
Dominance

1
0 0.2 0.4 0.6 0.8 1 1.2
Cation/Anion Ratio

Figure 6: Gibbs plot showing major processes groundwater which is in the order of (relative abundance
+ + 2+ 2+
controlling groundwater chemistry of cations is: Na +K > Ca > Mg ; while the relative
- - 2-
Ionic concentration of major elements present in abundance of the anions is: Cl > HCO3 > SO4 ) as
groundwater were analyzed for relative abundances and shown in figure 7. This suggest enrichment of ions from
ionic affinity. Schoeller plot was used to decipher the dissolution of diverse lithologic framework underlain the
relative abundance of ionic concentration in the study area, compared to ionic exchange phenomenon.

100.000
Water samples

10.000
Concentration (meq/l)

1.000

0.100

0.010

0.001
HCO3 SO4 Cl Mg Ca Na

Parameters

Figure 7: Scholler‟s classification for the hydrochemical components

HYDROCHEMICAL CHARACTERIZATION AND EVALUATION OF GROUNDWATER QUALITY 37
Simple mineral dissolution or ionic mixing processes is the rainy season. However, few of the samples plotted
mainly responsible for the variation in the within the „Ion Exchange‟ and „Reverse Ion Exchange‟
hydrochemistry of the water samples in the study area fields, indicating that the water in the study area has
as it depicted by the cluster of the data points plotting undergone partial mixing. The cluster of data
majorly in the simple dissolution or mixing rectangle groundwater sample points represents samples with
(Figure 8) which depicts a high rate of dissolution of similar composition of anions and cations (Figure 8).
chemical constituents usually experienced at the peak of

SO4

Water samples
80 20

60 40
3
CO

40 60
Cond
+
O3

1100

1300

1500
500

700

900
20 80
HC

Cl
80
Ca
60 Simple
1 2
dissolution
3
40
20 or mixing

Reverse
Mg

ion
4 5 6
exchange
80

60

Ion
7 8
40

exchange
9
20

7.6
K 7.5
a+ 7.4
pH_field

N 7.3
7.2
7.1
7.0
6.9
6.8
Figure 8: Durov‟s Plot of the Studied Water Samples

4.5 HYDROCHEMICAL CLASSIFICATION Majority of sample (85 %) falls in groups I and II which
The classification of groundwater facies was done using show evolved groundwater type where unique chemical
Piper‟s diagram (Piper 1944). The ternary diagrams masking is achieved through rock-water interaction, ion
(Figure 9) show the water samples in the study area are exchange within unsaturated zones; increased resident
basically „Alkali waters‟ with „Earth Alkaline‟ components time; and anthropogenic influences.
- -
that are predominantly HCO3 and Cl . The relative The group III water types representing meteoric
abundance of the three (3) dominant water types are: signatures or fresh recharged water constitutes only 5 %
Na-HCO3-Cl > Ca-Mg-HCO3-Cl > Na-Ca-Cl. The plots of the total samples. The location of the samples
of desirable data on the diamond-shaped field classify collected varies widely both vertically and spatially within
the groundwater types into three groups (Figure 9). the study area, suggesting precipitation as the major
source groundwater recharge.
38 SHUAIBU A. M., GARBA M. L AND ABUBAKAR I. Y.

Water samples
Dominant Water Type:
Na-HCO3-Cl 80 80

=>
60 60c
O4

<=
+S

Ca
1) Earth-alkaline waters
Cl

40 40

+M
a) Predominantly HCO3-
e b) HCO3- + SO42-

g
c) Predominantly SO42-
20 b 20
2) Earth-alkaline waters (with
alkali components)
Mg SO4 d) Predominantly HCO3-
a e) Predominantly SO42-
g
3) Alkali waters
80 80 f) Predominantly HCO3-
d g) Predominantly SO42- + Cl-

60 60

40 40
f
20 20
20

40

60

80
80

60

40

20

Ca Na+K HCO3+CO3 Cl

Figure 9: Piper‟s trilinear plot showing the different hydrochemical facies

The sodium hazard of the groundwater samples in the study area ranges from „Low‟ to „Very High‟, with most of the
samples plotting within the „Low‟ field; while the salinity hazard ranged from „Low‟ to „High‟ as shown in figure 10. This
indicate that the groundwater of the area can be used for plants having good salt tolerance and also indicate that it
suitable for irrigation purposes, in case of tube wells development.

C1 250 C2 750 C3 2250 C4

Water samples
30

Sodium (Alkali) hazard:

S1: Low
S2: Medium
S3: High
S4: Very high
Salinity hazard:
C1: Low
C2: Medium
Sodium Hazard (SAR)

C3: High
20 S4 C4: Very high

10
S3

S2

S1
0
100 1000
Salinity Hazard (Cond)
Figure 10: Wilcox plot of water samples
HYDROCHEMICAL CHARACTERIZATION AND EVALUATION OF GROUNDWATER QUALITY 39
5.0 CONCLUSION Akano, O. J, Idris-Nda, A and S. H. Waziri, 2015.
As far as suitability is concerned virtually all the studied Geology and Hydrogeology of Part of Suleja
cations and anions revealed average concentration North Central. J. of Scientific Research and
lower than the maximum permissible limit for drinking Reports 9(5): 1-15, DOI:
water by WHO, (2017). Though the compiled overall 10.974/JSR/2016/21577.
water quality index for the studied groundwater shows
„very poor water quality‟. These are due to the fact that Akujieze, C. N., Coker, S. J. L. and Oteze, G. E., 2003.
WQI rating reflect the composite influence of different Groundwater in Nigeria – a millennium
water quality parameters. Heavy metals such as iron, experience – distribution, practice, problems
lead and chromium show average concentrations that is and solutions. Hydrogeology Journal, 11, 259-
above the threshold of world health organization‟s 274.
standard for drinking water. Though the slight
contamination of those heavy metals does not call for Amadi, A. N., 2010. Effects of urbanization on
alarm, but constant monitoring is required to safeguard groundwater quality: A case study of Port-
further contamination of those metals. Harcourt, Southern Nigeria. Natural and Applied
The result of the multivariate statistical analysis, as Sciences Journal, 2010, 11(2): 143 – 152.
applied to the chemical data set of groundwater in the
Zamfara underlain aquifer, provides an insight into the Amadi A. N., Olasehinde P. I., 2008. Assessment of
underlying controlling Hydrochemical processes in the Groundwater Potential of parts of Owerri,
area. Five factors including factor-1 (total hardness, Southeastern Nigeria. J. Sci. Educ. Technol.
chloride, nitrate, manganese, bicarbonate and alkalinity), Vol.1 (2): 177-184.
factor-2 (TDS, conductivity, total hardness, magnesium
and calcium), factor-3 (Temperature, sodium, Andre, L.; Franceschi, M.; Pouchan, P.; Atteia, O., 2005.
potassium, copper, zinc, iron and chromium), factor-4 Using geochemical data and modeling to
(calcium, magnesium and nitrate) were extracted from enhance the understanding of ground water flow
the data-set represents the signatures from dissolution in a regional deep aquifer, Aquitaine Basin,
of bedrock through which the groundwater passes, ionic south-west of France. J. Hydrol., 305, 40-62 23
mixing, leaching from the lateritic overburden, pages.
agricultural activities (fertilizer application) and effluent
from waste dumpsites in the area. Out of 86.43% of the Apha. 1995. Standard methods for the Examination of
total variance in the dataset, ionic enrichment coming Water and Waste Water APHA. In American
from natural means accounts for 69.63%. The porosity Public Health Association. (Ed.), Manual of
and permeability of the aquifer system in the area allows Water Quality Analysis (p. 1467). Washington,
for groundwater movement of contaminant from one DC.
point to another. The remaining 16.80% is attributed to
manmade factors like farming activities and poor land- Arabi A. S; Kwaya, M. Y; Garba, M. L; Funtua, I.I; and
use system prominent in the area. Dewu, M. B. B., 2012: Qualitative
The distribution of major ions in the groundwater is as Evaluation of Groundwater from parts of Upper
+ + 2+
follows: relative abundance of cations is: Na +K > Ca Benue River Basin for Compliance with
2+ -
> Mg ; while the relative abundance of the anions is: Cl Regulated Guidelines. International Archive of
- 2-
> HCO3 > SO4 . Groundwater of the Zamfara aquifers Applied Sciences and Technology Volume 3 (1)
are majorly of evolved type with mixing of ionic March 2012: 46 – 53,
concentrations. Alkalis are more in abundant that www.soeagra.com/iaast.htm.
alkaline earth, while Cl and HCO3 dominate SO4 and
NO3. The water samples in the study area are basically Cronin, A. A.; Barth, J. A. C.; Elliot, T.; Kalin, R. M.,
„Alkali waters‟ with „Earth Alkaline‟ components that are 2005. Recharge velocity and geochemical
- -
predominantly HCO3 and Cl . The relative abundance of evolution for the Permo-Triassic Sherwood
the three (3) dominant water types are as thus: Na- sandstone, Northern Ireland. J. Hydrol., 315 (1-
HCO3-Cl > Ca-Mg-HCO3-Cl > Na-Ca-Cl. Simple mineral 4), 308-324 17 pages.
dissolution or mixing processes is mainly responsible for
the variation in the hydrochemistry of the water samples Davis J. C., 1973. Statistics and data analysis in
in the study area. geology. John Wiley and Sons, Inc. New York,
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