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Impact of Water-Rocks Interaction on Groundwater Geochemistry of Southern Mor Range, Balochistan, Pakistan and its Appraisal for Drinking Water Quality.

Byline: Maria Kaleem, Shahid Naseem, Erum Bashir, Bushra Shahab and Muhammad Mansha

Summary: Major and trace element geochemistry of groundwater of southern Mor Range, Balochistan was made to insight the impact of igneous and sedimentary rock on the composition of groundwater. The median values of ions display Na+> Mg2+ >Ca2+>K+ and HCO3->SO4-2>Cl->CO3-2 trend in the distribution of cations and anions respectively. The plots on Piper diagram indicated Ca-Na-Cl-type water (40.84%) as dominant water facies, followed by Ca-Cl-type (18.36%), Ca-Na-HCO3-Cl-type (16.33%), Ca-HCO3-Cl-type (12.24%), Na-Cl is (10.20%). The plots on Gibbs' diagrams delineate rock weathering combined with evaporation process for regulating the ionic composition. Molar ratio of Ca2++Mg2+ vs. HCO3-+SO42- and Ca2+/Na+ vs. Mg2+/Na+ demonstrated that the groundwater of the study area has genetic association with the igneous rocks of Bela Ophiolite and sedimentary rocks of Ferozabad Group.

Strong correlation matrix and PCA diagram also witnessed genetic affiliation with the rocks of the study area. The ionic composition revealed, nearly 50% samples faced process of ion exchange. Estimation of selected trace elements (Fe, Zn, V, Mn, Cu, Pb, Cr, Ni, As and Co) was also done to evaluate the drinking water quality and their possible health implications. Majority of them was found within permissible limits; however, in some of the samples, Fe, V and Pb exceed the WHO specifications.

Key words: Geochemistry, Groundwater, Medical geology, Southern Mor Range, Trace elements, Water-rock interaction


Study area lies in the southern part of Mor Range in which both igneous (Bela Ophiolite) and sedimentary (Ferozabad Group) rocks of Mesozoic age are present (Fig. 1). The climate of study area is arid and the demand for fresh water has increased drastically for agricultural and domestic purposes. The rapid growth of population and development of industrialization in the area enormously increased the exploitation of groundwater. Major ions in groundwater are mainly organized by rock weathering and climatic factors. Other regulating factors are atmospheric input, anthropogenic activities and biogeochemical processes [1]. During the water-rock interaction, a very discrete assemblage of ions is dispersed in the surface and groundwater [2].

It is problematic to handle and understand large variation in the major and trace elements composition of groundwater due to variability in lithology, climatic factor and anthropogenic activities in an area. In addition to geochemical interpretations, multivariate statistical analyses are commendable to resolve complex mutual relation of the major and trace ions. [3].

Medical geology is an emerging discipline that relates impact of geomaterials (rocks, minerals, soils, water, etc.) on the human health and other biota [4]. Certain trace elements (micronutrients) like Fe, Mn, Zn, Cu, etc. are essentially required for the proper functioning of human body. Their deficiency or excess in the human system can promote several health disorders. On the other hand, some trace metals like Pb, As, Hg and Cd, are not desired for any biological functions and are toxic even in trace quantity [5].

Current work aims to present a systematic evaluation of groundwater geochemistry of southern Mor Range and surrounding areas to elaborate the influence of rocks on groundwater composition. Multivariate statistical analysis in form of PCA was used to support geochemical interpretations. One of the purposes of current study is to provide an understanding of the source and distribution of Fe, Zn, V, Mn, Cu, Pb, Cr, Ni, As and Co in groundwater; its suitability for drinking purpose and their potential health effects.


Representative 49 groundwater samples were collected randomly from different area under study (Fig. 1). Standard analytical methods [6] were adopted for the estimation of chemical and physical parameters. The pH, EC and TDS of the samples were checked on the spot, using Denver Instrument, Model 50. Gallenkamp FGA 350 L flame photometer was used for Na and K measurement. Estimation of chloride was done by means of a chloride meter (Jenway PCLM 3). Volumetric techniques were applied to analyze Ca, Mg, CO3, HCO3 and SO4. Concentrated nitric acid is used to acidify groundwater samples (~1% v/v) for the assessment of trace metals [7]. Trace elements were analyzed on ICP-MS (US-EPA 200.8) with detection limit of ~1ug/l. Borosilicate glassware and extra pure chemical reagents were utilized to reduce contamination during experiment. For precision and accuracy of analytical results, double deionised water of low conductivity (Zn>Mn>Pb>V>Cu>Ni>Co>Cr>As trend (Table-1). The trace element content of ground water shows good liaison with the igneous and sedimentary rocks of study area. The average abundance of some trace elements was high due to mineralization in the study area.

Ionic composition

Box-Whisker plots are quick and convenient way to visualize major ionic composition of groundwater (Fig. 2a). Additionally, in case of large variation in the analytical data, median values of ions demonstrate better concept on box diagram, instead of the average values. The median values of ions display Na + > Mg 2+ >Ca 2+ > K + and HCO 3 - >SO 4 2->Cl - > CO3-2 trend in the distribution of cations and anions respectively. Stiff diagram provides a rapid comparison of ionic composition and ionic balance of water. The average ionic composition on stiff polygon exhibits nearly equal moles of Na + -Cl - and Mg 2+ -SO4 2- and less Ca 2+ -HCO 3-, signifies variation in ions enrichment due to variant geochemical environment, prevailed in the study area (Fig. 2b).


The piper plot perfectly visualizes all major ions of a groundwater at a glance, presenting their concentration in form of milli-equivalent percentages on two separate equilateral triangles. It facilitates the concept of hydrogeochemical facies of groundwater, which interpret water-rock interaction and reveal major controlling factors.

Approximately 60% water samples have mixed-type cations, the remaining Na-K and Mg-type water are 20% each (Fig. 3). In the Cl - - SO42- -CO32- +HCO3 - triangle, all samples display scattering and majority of them are mix-type (57.14%), while 24.48% samples are Cl-type. The SO 42- and sum of CO 32- +HCO 3 are 14.28 and 4.08% respectively.

Classification scheme of [9] water-facies is adopted for present work. The sample plots in the central part of Piper diagram display dominancy of Ca-Na-Cl-type water (40.84%), followed by Ca-Cl-type (18.36%), Ca-Na-HCO 3 -Cl-type (16.33%), Ca- HCO 3 -Cl-type (12.24%) and Na-Cl is10.20% (Fig. 3).

Water-rock interaction

The plots on Gibbs diagrams indicate that the groundwater of southern Mor Range has significant impact of weathering with little contribution of evaporation (Fig. 4a and b). The K + /Ca 2+ ratio is also used to determine the degree of weathering and chemical changes. The K + /Ca 2+ ratio of present study varies 0.01 to 0.33, indicating variable degree of weathering and mobility of ions.

Work presented by [10] HCO 3 - +SO 42- vs. Ca 2+ +Mg 2+ scatter diagram to discriminate ionic contribution due to weathering from either silicate or carbonate rocks. The plots of present study lies on either side of the equiline (Fig. 4c), indicating that these ions contribute from the weathering of BO (30.61%) and rest from sedimentary rocks of FG. The molar ratio of Ca/Na vs. Mg/Na exhibits a linear trend between silicate-carbonate paths (Fig. 4d).

High Cl-/ IPSanions (>0.8) and low Na+/Na++Cl- (0.9) for Mn, Ni and Co (Fig. 6), reflecting their association with the ultramafic-mafic segments of BO. Zinc and Pb show affiliation with the rocks of FG and up to some extent from BO.

Current study area is comprised of rocks of diversified origin and composition. Impact of these mix rocks can be envisaged from the factor loadings and rotated space diagram. The PCA of studied samples is assessed based on six factors loadings, whose cumulative percent is 82.168 (Table-2).

Among these six factors, two (Factor 1 and 2) are dominated, controlling the entire geochemistry of the water. Probably these two factors representing lithological influence of igneous and sedimentary rocks individually. The variance percent of first factor is 30.53% and shows positive loadings of TDS (0.691), Ca (0.621), Mg (0.600), Na (0.562), SO4 (0.566) and Cl (0.565), inferring their genetic relation with the rocks of the study area. Such affiliation is also illustrated in the PCA rotated space diagram (Fig. 5). Second factor explained 23.051% of the total variance. The moderate negative loadings of second factor of TDS (-.693), Mg (-0.712), Ca (-0.595) and SO4 (-0.733) and Na (-0.431) is related to ion exchange mechanism, operative in aquifers (Table 2). In contrast to Na, K shows low negative loading, possibly due to its large ionic size, the exchange process is low.

It is important to note that K shows maximum positive loading (0.814) in the sixth component, probably due to the tholeiitic nature of the BO. The good positive loadings of Mn, Ni, Co, Zn and Pb for both first and second components also evidences for its alliance with the varied igneous and sedimentary rocks and associated mineralization of study area, it is also visualized on the rotated space diagram (Fig. 5). The third factor amplifying 11.36% of the total variance shows moderately high-positive loadings for V (0.741), As (0.608), Na (0.612) and Cl (0.510). Factor 4 is only representing CO3 (0.733) even though it doesn't have any significant relation with other parameters except Cu (0.477). Factor 5 also reveals control on HCO3, Cu and Fe with loading values -0.626, 0.526 and 0.539 respectively, probably due to cupric/cuprous and ferric/ferrous ions in the water at varying alkalinities. Factor 6 shows maximum loadings for K (0.787) with moderate loadings of Cr (0.599).

However, PCA-based diagram (Fig. 5) plots V, Cr and pH as separate population possibly this is due to the amphoteric nature of V and Cr and as both are capable to form anions in the groundwater at variable alkalinity (pH).

Table-2: Variance of rotated R-mode factor loading matrix in PCA



V###-0.214###0.124###0.741 -0.229###0.039###-0.065

Cr###-0.339###0.147###0.371 -0.252###0.088###0.599

Mn###0.769###0.625###-0.050 -0.043###0.007###0.025

Co###0.765###0.631###-0.041 -0.039###-0.010###0.029


As###0.457###0.244###0.608 -0.111###-0.027###-0.065

Pb###0.753###0.639###-0.029 -0.015###-0.018###0.005

Fe###0.454###0.010###-0.421 -0.246###0.539###-0.034

Ni###0.803###0.578###-0.063 -0.021###0.013###-0.008

Zn###0.759###0.639###-0.034 -0.036###-0.014###0.028

TDS###0.691###-0.693###0.144 -0.061###-0.052###0.026



Mg###0.600###-0.712###-0.138 -0.136###0.075###0.047

Na###0.562###-0.431###0.612 -0.018###-0.151###0.018





SO4###0.566###-0.733###-0.068 -0.214###0.129###0.065

Variance % 30.535###23.051###11.361 6.153###5.711###5.357

Cumulate % 30.535###53.586###64.948 71.101###76.811###82.168

Trace elements

Sedimentary rocks of FG (Jurassic) have Mississippi valley type (MVT) and Sedex type sulphide mineralization, in which Zn, Pb, Cu and barite are important. The igneous rocks of BO (Cretaceous) are also rich in trace elements and at places showing small to medium size deposits of Cr, Fe and Mn. The minimum, maximum and average trace metal concentrations in different parts of the southern Mor Range, Balochistan has been presented in Table-1 and its suitability for drinking water with reference to [14] is displayed in Fig. 6.

Iron (Fe)

Iron in the groundwater of the study area range from 440-3884ug/l with a mean of 1894ug/l (Table 1). It is mainly derived from the weathering of ophiolitic rocks of the study area, though some part is also related to sedimentary rocks. The guideline for Fe in the drinking water is not properly documented in the literature [14], however according to [15] the maximum allowable and the permissible concentration in drinking water should be within 300-1000ug/l. In the study area, nearly 86% samples have exceeding quantity of Fe (Fig. 6). High iron in drinking water may raise the palpitation, hypertension, drowsiness and coagulation of blood in the arteries [16]. Excessive amount of Fe may be responsible for diabetes mellitus, hepatic fibrosis and risk for several types of cancers.

Zinc (Zn)

The high concentration of zinc in the groundwater is mainly attributed to the rocks of FG of Jurassic age in which Zn-Pb-barite mineralization is common. Zinc shows wide range of concentration in the groundwater (10-64434ug/l) of study area. The amount of Zn in all studied samples is within the specified limit of 3000-5000ug/l [14], except in sample number 23 (Fig. 6). Zinc is one of the essential trace elements that play a vital role in the physiological and metabolic process. Deficiency of Zn may make a person more susceptible to disease and can cause cosmetic problems, such as, skin, nail and hair [17]. On the contrary, excess Zn also has adverse and severe toxic effects and may interfere in the physiological process in the human body.

Vanadium (V)

The average crustal abundance of V is 135mg/kg; found more in mafic and ultramafic rocks. In magmatic rocks, V may exist as V3+ ion and are compatible with Fe3+ bearing rocks. Vanadium is very low (0.9ug/l) in stream water but its mobility is high. The average value of V in all the collected samples of the study area is 19ug/l (Table 1).

Probably low V in the groundwater of study area is due to alkaline pH (av. 7.89) because the concentration of V in sub-oxic groundwater decreased with increasing pH [18]. Vanadium in little amount stimulates insulin formation activity, however high V (>15ug/l) in drinking water may pose health risk [19]. Nearly 39% of the studied samples have concentration of V above the maximum permissible limit of 15ug/l (Fig. 6).

Manganese (Mn)

The pillow basalt of BO contains small to medium size Mn deposits in the area. In nature, it is capable to exist in oxidation states from -3 to +7 and its mobility in aqueous phase largely depends upon the oxidation state. The mean abundance of Mn in stream water is 7ug/l, due to its poor mobility [20]. In the study area, Mn has been noted in groundwater at concentrations from 5 to 1942ug/l with a mean value of 59ug/l (Table 1). The [14] has established a good health based value of 50ug/l and maximum permissible concentration is set at 400ug/l. The studied samples have ideal range of Mn in drinking water and are safe with respect to Mn toxicity.

Copper (Cu)

In the study area, Cu is derived in the groundwater both from igneous and sedimentary rocks. The mean concentration of Cu in ground water is 16ug/l. In nature, copper commonly occur either as divalent (Cu2+) or monovalent (Cu+). In acidic environment the mobility of copper is high and it reduced to Cu+ or Cu0 and forms insoluble sulphides, oxides and elemental Cu [21]. Owing the minor Cu mineralization, the studied water samples are Cu deficient (4-48ug/l). Even the maximum value of Cu is much lower than the WHO prescribed value (2000ug/l) in drinking water [14]. Copper is an essential life nutrient, required in minute quantities for healthy growth. At higher concentration, it affects stomach and intestine; cause anemia and damage to liver and kidney.

Lead (Pb)

In the southern Mor range, small deposits of galena are associated with the FG rocks of Jurassic age. On weathering, galena (PbS) slowly disintegrates and accumulate in the down slope soil and water. The amount of Pb is very low in surface water (3ug/l) and the concentration may exceed high in the mineralized areas. In the study area, the content of Pb varies from 1 to 512 with a mean of 20ug/l (Table 1). High Pb bearing water is due to lead mineralization in the Southern Mor Range. Nearly 24% water samples are more than the maximum permissible concentration (10ug/l) of lead in the drinking water [14]. Lead is a very toxic element which gradually accumulates with age in many organs of humans (bones, liver, kidney and spleen) and can harm liver, kidney and nervous system [22].

Chromium (Cr)

The concentration of Cr in the groundwater is very low 1ug/l [20], it is also noted low (1 to 32ug/l) in the groundwater of study area (Table 1). The Cr display dual behavior on human health, Cr3+ is an essential human nutrient. It also helps to maintain good lipid balance between high-density lipoprotein (HDL) and low-density lipoprotein (LDL) [23]. Chromium also regulates the glucose/insulin metabolism and its deficiency may cause the type-II Diabetes. It is important to note that none of the collected water samples exceeded the maximum permissible limit of 50ug/l stipulated for Cr in the drinking water [14].

Nickel (Ni)

The olivine rich ultramafic rocks often associate with Ni minerals. The lower segments of BO contain elevated amount of Ni. After weathering, Ni is incorporated in water but its concentration seldom exceeds in the groundwater due to its low mobility in the aqueous phase [20]. Despite the presence of ultramafic rock, the abundance of Ni in the collected samples is low. It ranged from 2 to 130 with an average of 10ug/l (Table 1). In the study area, the abundance is low, except in one sample (# 23), the remaining samples are within the permissible limit of 20ug/l for drinking water [14].

Arsenic (As)

Arsenic occurs in trace quantities in the water 2ug/l. The groundwater samples of study area have 1 to 16 with a mean of 4ug/l. All the sample are within the specified limit of 10 ug/l [14], except samples collected from 23 and 48 locations (Fig. 1). Probably As is derived from sulphide deposits of FG. Arsenic concentration in ground water up to (500ug/l) is carcinogenic; it is a source of bladder, skin and lungs cancer [24].

Cobalt (Co)

Concentration of Co in the stream water is ~0.1ug/l but in some cases, it may reach up to 5ug/l. The minimum and maximum concentration of cobalt in studied samples is 1.0 and 365ug/l respectively. Maximum admissible limit of Co for drinking purpose is not mentioned by [14], however it is set at 40 by many drinking water agencies. All the samples are below the maximum admissible limits of cobalt in drinking water, except one sample. Cobalt is essential in trace amounts for humans and other organisms. It is an integral part of the vitamin B12 complex, other benefit of cobalt is stimulation in production of red blood cells [25].


Majority of groundwater samples of southern Mor Range are slightly alkaline (av. pH 7.89) and saline (av. TDS 1105mg/l); show inverse relation among pH and TDS. The median values of current study display Na + > Mg 2+ >Ca 2+ > K + and HCO 3 - >SO 4 2- >Cl - > CO 3 -2 trend for cations and anions respectively. The average ionic pair analysis on stiff diagram signifies nearly equal moles of Na+K-Cl and Mg-SO 4 , while Ca-CO 3 +HCO 3 are less. The plots on Piper diagram indicated Ca-Na-Cl-type water as dominant water facies, followed by Ca-Cl-type, Ca- Na-HCO 3 -Cl-type, Ca-HCO 3 -Cl-type and Na-Cl type.

Low Cl - / IPSanions (av. 0.39), low K + /Ca 2+ ratio (av. 0.08) and high HCO 3 - /Cl - ratio (av. 1.32) is indicative of rock weathering dominancy in the study area. The plots on the Gibbs diagrams (Na+K/Na+K+Ca) and (Cl/Cl+HCO 3 ) vs. TDS (mg/l) suggest that groundwater of southern Mor Range area has more influence of rock weathering with some contribution of evaporation. The assumption of rock weathering is further evidenced on total base metal (Zn, Cu, Pb, Cd, Ni, Co) vs. pH and classifies the nature of groundwater as near neutral and low base metal.

Based on positive (48.97%) and negative (51.02%) Chloro Alkaline Indices 1 and 2, it is assumed that the groundwater of the study area has suffered the process of ion exchange.

Strong correlation matrix among major and certain trace elements in water pinpoint their affiliation with the rock and minerals. Loadings of both factor 1 and 2 revealed dominant control of igneous and sedimentary rocks separately on the geochemistry of groundwater; which is also illustrated in the PCA rotated space diagram as separate groups. Loadings of other factors in PCA shows impact of ion exchange mechanism and alkalinity. Quantity of Zn, Mn, Cu, Cr, Ni, As and Co in studied samples is within the specified limit of WHO for drinking. In some of the samples, Fe, V and Pb exceed the permissible limit of WHO specifications.


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Author:Kaleem, Maria; Naseem, Shahid; Bashir, Erum; Shahab, Bushra; Mansha, Muhammad
Publication:Journal of the Chemical Society of Pakistan
Article Type:Technical report
Geographic Code:9PAKI
Date:Apr 30, 2019
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