Journal of Water Research. 138 (2017) 300-325 https://sites.google.com/site/photonfoundationorganization/home/journal-of-water-research Original Research Article. ISJN: 3294-9473: Impact Index: 4.62

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Journal of Water Research

Evaluation of ground water quality, hydro chemical facies and ionic ratios in Kom Hamada City, Al-Beheira Governorate (Western Nile Delta), Egypt Zayed M. A.*a, Elhdad A.M.A.b a b

Chemistry Department, Faculty of Science, Cairo University, Cairo, Egypt Madina Higher Institute of Engineering and Technology, Giza, Egypt

Article history: Received: 26 October, 2016 Accepted: 27 October, 2016 Available online: 19 January, 2017 Keywords: Groundwater quality, Hydrochemical faceis, Groundwater types, Ionic ratios, Ion exchange, Kom Hamada City, Beheira, Egypt Corresponding Author: Zayed M.A.* Prof. Dr. (D.Sc.) Email: Mazayed429 ( at ) yahoo. ( dot ) com ElhdadA. M. A. Ph.D

Abstract Evaluation of ground water in Kom Hamada city, Southern Egypt: quality, hydro chemical facies and ionic ratios has been carried out. Physico-chemical parameters of different wells at different zones were analyzed. The values of all parameters for wells under consideration are less than the maximum permissible limits except wells numbers 13, 14 and 15; which have high manganese and ironvalues of non-permissible limits. Removal of iron and manganese is recommended before using these wells for drinking.Pipe r tri-linear diagram for the studied area

shows mixture of three types of water with variable concentrations of major ions; such as Ca – HCO3- , Ca – Na – HCO3-, and CaCl. According to the Sulin's system, the wells are characterized by sodium sulfate and magnesium chloride genetic water types. It is very important to give comprehensive and accurate hydro chemical knowledge in the study area. Owing to the hydro geological heterogeneity in order to evaluate the hydro chemical characteristics, it is important to determine the ionic interactions as well as the hydro geochemical facies distribution in the area. Achieving these aims will result in establishment of developing an appropriate monitoring programme and therefore improved management of the groundwater resources of the area. This research aims chiefly to find new underground water resources as alternative of limited River Nile source to overcome problem of increasing population rate in Egypt. Citation: Zayed M.A.*, ElhdadA. M.A., 2017. Evaluation of ground water quality, hydro chemical facies and ionic ratiosin Kom Hamada City, Al-Beheira Governorate (Western Nile Delta), Egypt.Journal of Water Research. Photon 138, 300-325. All Rights Reserved with Photon. Photon Ignitor: ISJN32949473D848019012017

1. Introduction Water is the most important natural resource and it is vital for all life forms on earth. Depending on its usage and consumption, it can be a renewable or a non-renewable resource. Recently, Water demand has increased rapidly with the construction of energy, development of industry, agriculture, urbanization, improvements in living standards and eco-environment construction. Ground water is an important source of water supply throughout theworld; the most important reasons are the nonavailability of potable surface water (Pichiah et al., 2013) Water quality refers to the physical, chemical and biological characteristics of water (Santhoshand Revathi, 2014). The quality of ground water is controlled by several factors including climate, soil characteristics, rock types, topography of the area, human activities on the

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Groundwater,…etc. (Cloutieret al., 2008;Prasanna et al., 2010). Ground water availability and quality has become the source of concern for researches worldwide. Most of these studies focused on the salt water intrusion (Mtoni et al., 2013; Triki et al.,2014), ground water salinization (Trabelsi et al., 2007; Cruz et al., 2010; Ahmed et al., 2013; Chaudhuri et al., 2014), arsenic and other heavy metals in ground water(Guo et al., 2008; Nouri et al., 2008; Shah et al., 2013; Pradhan et al., 2014), the sustainability of aquifer exploitation (Suet al., 2014) and ground water quality evaluation (Mudiam et al., 2012). The chemical composition of ground water is controlled by many factors, including the composition of the precipitation, geological structure and mineralogy of the watersheds and

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aquifer and the geological processes within the aquifer. The interaction of all these factors leads to various water types. In many areas, particularly arid and semi-arid zones, ground water quality limits the supply of potable fresh water. To utilize and protect valuable water resources effectively and predict the change in ground water environments, it is necessary to understand the hydro chemical characteristics of the ground water and its evaluation under natural water circulation processes (Lawrence et al., 2002; Edmunds et al., 2006). The hydro chemical processes and hydro geochemistry of the ground water vary spatially and temporally, depending on the geology and chemical characteristics of the aquifer. Hydro geochemical processes such as dissolution, precipitation, ion exchange processes and the residence time along the flow path control the chemical composition of the ground water (Nwankwoalaand Udom, 2011). The time available for water rock interactions, and hence the chemical composition of water, strongly varies depending on the flow path and storage location of the water. The flow path and residence time also influence the contaminant fate (Younes, 2012). The hydro geochemical processes of the ground water system help to obtain an insight in to the contributions of rock / soil-water interaction and anthropogenic influences on ground water. These geochemical processes are responsible for the spatiotemporal variations in ground water chemistry (Chebbahand Allia, 2015). The increase of knowledge of geochemical processes regulates the ground water chemical constituent's.This well help to understand the hydro chemical systems for effective management and utilization of the ground water resource by clarifying relations among ground water quality and quantifying any future quality changes (Srinivasamoorthy et al., 2014). The Nile delta aquifer, with its eastern desert fringes, extends to over 22,000 km2. Along the western fringe of the Nile delta, there was the first reclamation project in Tahrir area (more than 50 years ago).The available water resources include surface water (Rosetta branch and its irrigation channels) and relatively shallow ground water that is mainly recharged from the surface water. Ground water is the main source for domestic, industrial

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and agricultural use in the western Nile delta region (Dawoud et al., 2005). The western Niledelta contains four main ground water aquifers: the water bearings formations belong to the Quaternary, Pliocene, Miocene and Oligocene (Sharaky et al., 2006). The main objectives of this research included the study of Wadi El Natrun and Wadi El Farigh, which have been established and subjected to future extensions. Limited water resources are the main problems to achieve the main target of constructing new settlements and land reclamation projects for sustainable development in the western Nile delta. 2. Experimental 2.1. Monitoring sites Western Nile Delta region is located between 290 30\\to 310 00 \ \ E and 30 0 00 \ \ to 31 0 00 \ \ N. It occupies the area between Cairo at equator and Alexandria, west of Rosetta branch, and extends westward to the desert area from the west of Wadi el-Natrun up to the eastern edge of the Qattara Depression. Topographic data is available from survey maps of scale 1:100,000 for most of Nile Delta area. The elevation of the area ranges from (0.00) mean sea level in the north to (150.00) above mean sea level in the south. The existing irrigation networks in the study area consists of six main irrigation canals, namely the Rosetta branch, Rayah Behiri, Rayah Nasery, Nubaria canal, Mahmoudia canal and El Nasr canal. The climate of the study area can be classified as predominantly Mediterranean. The average temperature varies from 14 to 32oC in months of July and August. The location of Western Nile Delta is shown in Figure1. Beheira governorate is a costal governorate in Egypt, it is located in northern part of the country in the Nile Delta, and its capital is Damanhur. Beheira governorate enjoys an important strategically place in west of the Rosetta branch of the Nile. It is bounded by Mediterranean (north), by Alexandria Governorate ( north western), by Matrouh Governorate (west), by Giza (south Western), by Menoufia(east) and by Kafr Al Sheikh governorate (north eastern) ; two main Roads runs through the Beheira Governorate are Cairo-Alexandria desert Road and agricultural Road(Figure 2).

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Figure 1: Domain of Study – Western Nile Delta

Figure 2: The geographical location of Al- Beheira governorate

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2.2. Collection and analysis of water samples Fifteen wells of different villages in Beheira governorate were selected for the studies, (Table 1). Water samples were collected using poly ethylene bottles which were washed with tap water at the first and then were rinsed using double deionizes water. The water samples were collected from varies places at the studied area. Temperature, pH, E.C, and TDS were measured immediately. Then the samples were transported to the laboratory for further analysis after its treatment with 0.5 % chloroform as a preservative material (APHA, 2012). For analysis, all the instruments were calibrated appropriately according to the commercial grade calibration standard prior to the measurements. The samples were analyzed for pH, total hardness (TH), calcium hardness (CaH), magnesium hardness (MgH), electrical conductivity (EC), total dissolved solids (TDS), Calcium (Ca2+), Magnesium (Mg2+), Sodium (Na+), Potassium (K+), Bicarbonate alkalinity (HCO3-), Carbonate (CO32-), Chloride (Cl-), Sulfate (SO42-), NO3-, dissolved inorganic orthophosphate, silica, iron and manganese using the standard methods by the American Public Health Association (APHA, 2012) . The taste, color, odor, and turbidity were observed organoleptically. Table 1: Locations of wells under consideration Well NO. Location 1 Kafr El Ais 2 Kafr El Ais 3 Kafr El Ais 4 KafrSalamon 5 KafrSalamon 6 KafrSalamon 7 KafrSalamon 8 Abo Elkawe 9 Abo Elkawe 10 Demishly 11 Demishly 12 Demishly 13 Alkam 14 Alkam 15 Alkam

3. Results and Discussion 3.1 Assessment of groundwater quality for drinking purposes Tables (2 and 3) show the results of analysis of the water samples. The physicochemical parameters of the ground water quality data were statistically analyzed and the results were recorded in Table 4 in form of minimum, maximum, mean and standard deviation. The pH values ranged between 7.2 in well (1) and 7.9 in well (9) and indicate alkaline water in all wells under study. Generally the deviations in the pH value from 7 are primarily the result of the hydrolysis of salts not originated from Ph ton

strong bases and strong acids (Masoud et al., 2003). The pH values generally encountered may be largely due to the influence of the soils and organic matter (Orajaka, 1972; Zayed and El Hdad, 2016). All samples of all wells in all zones are colorless, odorless, and tasteless. The results give the abundance of the cations in the following order: Ca2+>Na+ >Mg2+ > K+, while those of the anions were in the following order: HCO3-> Cl-> SO42-> CO32-> PO43-> NO3-.Calcium is the dominant cation in the ground water of the study area, its concentration ranges from 44 to 104 mg L-1, with mean value of 72.32 mg L-1. The high value of calcium concentration was recorded in well (2), these high values of calcium concentrations, probably due to: i) the discharge of calcium rich effluents, ii) domestic, agricultural and industrial wastes, iii) microorganisms may favor the precipitation of calcium carbonate, iv) bacteria may decompose organic compounds containing calcium, as a result calcium carbonate produced by carbon dioxide formed during its decomposition (El Hdad, 2006). The decreasing of calcium content (<50mg L-1) is due to the seepage of freshwater from the river Nile and irrigation system (Sharaky et al., 2007). However, the World Health Organization (WHO, 2011) does not list guideline for this element in drinking water. According to Egyptian Ministry Health (EMH) Water Quality Standards (EMH, 2007) the values of calcium concentration for all wells in our study zones are below the recommended guidelines of Egypt (200 mg L-1). The distribution of calcium in aquatic habitats has attracted the attention of several investigators as it is the major constituent of mineral deposits as well as the shells and skeletons of organisms (Abdel Moati, 1985). Calcium is the form of calcium carbonate or sulfate resulting from organic activity or inorganic precipitation. The concentration values of magnesium of the wells at the studied zones are in the range between 19.6 mg L-1and 41.65 mg L-1, with mean value of 36.628 mg L-1. The increasing of magnesium concentration may be due to mixing with of Moghara aquifer (WHO, 2011).Leaching processes of clay that is lagoon and marine in origin add more magnesium (El Abd, 2005). According to the listed recommendation of World Health Organization (WHO, 2011), the maximum acceptable level of magnesium in drinking water is 50 mg L-1. Due to Egyptian Ministry Health (EMH) Water Quality Standards (EMH, 2007), the maximum acceptable level of magnesium in drinking water is 150 mg L-1, and therefore, all wells at our study zones are suitable for drinking purposes.

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Sodium is found in amount from 36 to 120 mg L-1, with mean value of 66.4 mg L-1. The minimum value of sodium concentration was recorded in well (15), while the maximum value was recorded in well (7). The high values of sodium concentration may be due to excess of bicarbonate ion which cause a release of the alkali ions (usually sodium Na+ ) into the water by exchanger such as clay materials and other related minerals that form part of the aquifer minerals (Olayinka, 1999). The values of sodium concentration in all wells under consideration are below the listed recommendation of World Health Organization (WHO, 2011)standards (200 mg L-1) and Egyptian Ministry Health (EMH) Water Quality standards(EMH, 2007) (200 mg L-1). Potassium with concentration valuesare ranged from 6.00 mg L-1 in well number 3 to 24 mg L-1 in well number 7, and the mean value is 12.4 mg L-1. The High level of potassium may be attributed to the ground water contaminated by Potassium fertilizers(El Hdad, 2006). The World Health Organization (WHO, 2011) and Egyptian Ministry Health (EMH) Water Quality standards (EMH, 2007) do not list a guideline for potassium in drinking water. Bicarbonate dominates the anionic components of the ground water under consideration, the bicarbonate concentration in the ground water under consideration are ranged between 220mg L1 of well (4), and 420mg L-1 for well (2).The source of the bicarbonate in the wells can be attributed to the carbon dioxide gas which renders the ground water slightly acidic by the formation of carbonic acid. This subsequent dissociation (Masoud et al., 2003) produces H+ and HCO3-. The values of carbonate ion concentration are low for all wells under study. The values of chloride concentrations were observed in the range between 32 mg L-1for well (4) and 110 mg L-1for well (11), with mean value of 78.266 mg L-1. The high Cl-value may be due to leaching from upper soil layers and inputs from domestic, agricultural runoffs (Das A., et al., 2015).The values of chloride concentration in all wells under consideration are lower than 250 mg L1 , therefore the water of all wells under study are tasteless and suitable for drinking purposes according to World Health Organization (WHO, 2011) standards (250 mg L-1), and Egyptian Ministry Health (EMH) Water Quality standards (EMH, 2007) which is (500mg L-1). The presence of sulfate in drinking water may cause noticeable taste and contribute the corrosion of distribution system (WHO, 1993).Table 2.2 shows the values of sulfate concentration as a range Ph ton

from 4.00 to100mg L-1 in wells 4 and 10 respectively, with mean value of 61.33 mg L-1. The higher value of sulfate in water can be attributed to the salt water intrusion to the aquifer (Masoud, 2003). However, the sulfate value for all wells under investigation is below the listed recommendation of WHO (2011) standards (250 mg L-1) and below the Egyptian Ministry Health Water Quality (EMH, 2007) standards(400 mg L-1). Hardness of water limits its use for domestic, industrial and agricultural activities. Water hardness can cause scaling of pots, boilers and irrigation pipes; it may also cause health problems to humans such as kidney failure (WHO, 2008).Water hardness mainly depends upon the amount of calcium or magnesium salts or both (Sirajudeen et al., 2014). In the present study the total hardness values varied from 250 mg L-1 in well (8) to 430mg L-1in well (2), with mean value of 330.4 mg L-1.The total hardness values of all wells lower than the prescribed limit of World Health (WHO,2011) Organization(500 mg L-1), and Egyptian Ministry Health (EMH, 2007) Water Quality Standards(500mg L-1). Table 4 indicates that the ground water under consideration ranged from hard to very hard water (Sawyer and Cartly, 1967). The majority of wells of the study area are characterized by very hard water while the remaining wells (4, 5, 8, 9, 13, and 15) are characterized by hard water. The high total hardness would lead to heart disease and kidney stone formation (Sirajudeen et al., 2014). Calcium hardness in our study ranged between 110 mg L-1 for well (4) and 360 mg L-1 for well (2). Also magnesium hardness in all wells under consideration was ranged between 80 mg L-1for well number 13 and 170 mg L-1for wells (2, 3, 4,5,6,10,11, and 12). An increase in the total solids content (TDS) of the ground waters is subjected to fertilizer input results from the almost total solution of the mineral part of many fertilizers, such as sulfates, that are not taken up by plants. Other fertilizer components, such as potassium and phosphorous can be found in water (Masoud et al., 2003). Salts of calcium, magnesium, sodium and potassium present in irrigation water may pose to be injurious to plants (Obiefuna and Sheriff, 2011). The authors went further to stress that salts from the major ions when present in excess quantities can affect the osmotic activities of the plants and may prevent adequate aeration (Ishaku et al., 2011). According to maximum permissible limit of TDS are set by World Health Organization (WHO, 2011) and Egyptian Ministry Health Water Quality Standards

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(EMH, 2007), all the wells are safe for drinking purposes. Nitrate (NO3-) is the most common groundwater pollutant worldwide (Spalding and Exner, 1993) and it is also the form of inorganic nitrogen that is most prevalent under freshwater, toxic conditions. It can enter groundwater from several sources, both natural and anthropogenic. The main natural source of nitrate is nitrogen fixation, in which relatively inert nitrogen gas from the air (N2) is converted biologically to ammonia (NH3) and organic nitrogen, which, in turn, are converted to nitrate by nitrifying bacteria in the soil. Some species of plants, microorganisms, and cyanobacteria are capable of nitrogen fixation. The majority of nitrogen-fixing plants are in the legume family (Fabaceae), and their ability to fix nitrogen comes from a symbiotic association with rhizobia, bacteria that live in their root nodules. This nitrogen then enters the soil and undergoes various transformations there. In pristine environments where natural soil nitrogen is the only source of nitrate in groundwater, nitrate concentrations in groundwater are typically (Mueller et al., 1996;BurkartandStoner, 2002) less than 2 mg L-1; however, in certain areas, such as the Sahel region of Africa, naturally occurring groundwater nitrate concentrations can be much higher (Edmunds and Gaye, 1997). Areas affected by human activities usually have much higher groundwater nitrate concentrations. These concentrations can originate from different sources, such as sewage leaks, chemical facilities, or animal feedlots (Gardner and Vogel; 2005, Wakida and Lerner, 2005). Numerous studies (Carpenter, et al., 1998; Nolan, 2001; Choi, 2007) have linked the raise of nitrate concentrations in groundwater to high population densities and urban development. The nitrate concentration values of ground water wells under consideration are reported in Table 2.2. The values are ranging from 0.01mg L-1 to 0.20mg L-1 for wells (1) and (13) respectively with mean of 0.0738mg L-1. Nitrate concentration increase with a respective increase in water hardness, chloride, sulfate and total solids (El Hdad, 2006). The low nitrate concentration in the ground water has been attributed to slow oxidation of nitrogenous compound. The variability in nitrate concentrations may be due to the difference in the rate of manure and nitrogen compounds applications (El Hdad, 2006). All the wells under consideration have nitrate concentration values below the list recommendation (44 mg L-1) of the World Health Organization (WHO, 2011) and Egyptian Ministry Health (EMH, 2007) Water Quality standards (44 mg L-1).

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Dissolved inorganic phosphorus, typically in the form of phosphate (PO43-), can enter groundwater from dissolution of the minerals making up the aquifer substrate, decomposition of organic matter in soils, or anthropogenic activity. Similar to nitrate, phosphate concentrations in groundwater are often considerably higher than in surface waters. For example, in Tomales Bay, California, groundwater phosphate concentrations reached 5.3 mg L-1, while the highest surface water concentrations (Oberdorfer et al., 1990) were<0.1 mg L-1. However, at other locations (Knee et al., 2008) such as Hanalei Bay, Kaua`i, groundwater and surface water phosphate concentrations were similar. Phosphate in groundwater often forms insoluble inorganic compounds that sorb to rock and particle surfaces(Wong et al., 1998). Thus, a larger proportion of this nutrient is retained by the aquifer substrate, and less is dissolved in groundwater. However, under certain circumstances, such as in sandy soils with low phosphate sorption capacity or when very high phosphate loads are added, phosphate can be transported by groundwater flow (Wong et al., 1998; Peaslee and Phillips, 1998). Two main sources of high anthropogenic phosphate loads are wastewater or sewage plumes and inorganic fertilizers (Knee and Paytan, 2011). The phosphates concentrations in the wells under consideration are recorded in Table 2.2, andthe lowest value was observed in the wells(2, 3,4,5,6,7,8,9,10,11,and 12), while the highest value was found in all remaining wells. The decrease of phosphate concentrations may be due to the availability of strongly soil absorption of phosphate ions (Seiler et al., 1988). The increase in phosphate ion concentrations can be attributed to agricultural activities (El Hdad, 2006). World Health Organization (WHO, 2011) and Egyptian Ministry Health (EMH, 2007) Water Quality Standards did not give a guideline value for phosphate ions. Silicon dissolved in groundwater exists as Si(OH) 4, commonly referred to as silica. The major source of silica to groundwater is the rocks, sediments, and soils making up the aquifer substrate. Silica concentrations in groundwater are less variable than those of nitrate, phosphate, or other dissolved constituents, with typical values (Davis, 1964) of about 17 mg L-, but varying somewhat based on rock type. Silica does not sorb to aquifer surfaces or react with other groundwater constituents (Haines and Lloyd, 1985). In contrast to nitrate and phosphate, the concentrations of which are influenced both by anthropogenic sources and by groundwater chemistry, groundwater silica

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concentrations are mainly determined by the mineral characteristics of the aquifer substrate (Davis, 1964) and how long the water has been in contact with that substrate (Haines and Lloyd, 1985). Silica in water is undesirable for a number of industrial uses because it forms scales in equipment, particularly on high pressure steam blades. Silica is removed most often by the use of strongly basic anion exchange resins in the deionization process, by distillation, or by reverse osmosis. Some plants use precipitation with magnesium oxide in either the hot or cold lime softening process (APHA, 2012). Silica values are ranging from 15mg L-1for wells (4 and 6) to 30 mg L-1 for well (13) with mean of 20.93 mg L-1.World Health Organization(WHO, 2011) and Egyptian Ministry Health (EMH, 2007) Water Quality Standards did not give a guideline value for phosphate silica. Iron is one of the most abundant metals in the earth's crust. It is found in natural fresh waters at levels ranged from 0.5 to 50 mg L-1. Iron may also be present in drinking water as a result of the use of iron coagulants or the rusting steal and cast iron pipes during water distribution (WHO, 1993). The main variable factors affected the solubility of iron include pH, redox potential (Eh), and concentrations of the dissolved carbon dioxide and sulpher species (Bodek et al., 1988; Mohamed, 2014). Iron is very rapidly precipitated from solutions with pH greater (EMH, 2007) than 5.5. As shown in Table 2.2, the values of iron concentration in the ground water wells are ranged between 0.05and0.80mg L-1., thus all wells are below the recommended guideline (0.3 mg L-1) of World Health Organization (WHO, 2011) except wells numbers 13,14, and 15. According to Egyptian Ministry Health (EMH, 2007) Water Quality Standards, the maximum acceptable level of iron in drinking water is (1.00 mg L-1), and all wells under consideration are below this level. The higher values of iron are mainly due to the effect of effluents discharged from the waste and domestic sewage (El Hdad, 2006).

Ministry Health (EMH, 2007) Water Quality Standards, the recommended level of manganese in drinking water is 0.50 mg L-1, thus wells numbers 13, 14, and 15 are with manganese contents greater than this recommended level. Manganese ion concentrations increased with rising ground water levels, then decreased as the water table dropped (Klinchuch and Defino, 2000). The higher concentrations of manganese in ground water may be due to manganese bearing minerals in contact with ground water under reducing conditions and active bacterial action, the presence of soluble form under the ground anaerobic conditions, the release from the sediment, and due to the biochemical transformation processes (El Hdad, 2006). Manganese is transformed through food chain from sediments to plants and animals then discharged directly or through decomposed products into water (El Hdad, 2006).Therefore, it is necessary to focus on the removal of iron and manganese from wells (13, 14 and 15) in an appropriate manner, such as the oxidation of iron and manganese by aeration method, then water is passed on sand filters to get rid of the deposited oxide

Manganese is one of the more abundant metals in the earth's crust and usually occurs together with iron. Dissolved manganese concentrations in ground and surface waters that are poor in oxygen can reach several milligrams per liter. On exposure to oxygen, manganese can form insoluble oxides that may result in undesirable deposits and color problems in distribution systems (WHO, 993).The range of manganese concentration in the wells under consideration is between 0.10 and 0.80 mg L1 . All the wells under consideration are with greater manganese contents than the recommended level in drinking water as listed by World Health Organization (WHO, 2011). According to Egyptian Ph ton

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Table 2: physical and chemical parameters of ground water samples for wells under consideration Well Color Taste Odor Temp. Turb. pH EC No. (oC) (NU) (µScm-1) 1 Colorless Tasteless Odorless 26 1.5 7.2 784 2 Colorless Tasteless Odorless 25 1.7 7.5 920 3 Colorless Tasteless Odorless 25 1.3 7.3 730 4 Colorless Tasteless Odorless 25 1.1 7.2 420 5 Colorless Tasteless Odorless 26 1.2 7.4 510 6 Colorless Tasteless Odorless 26 1.4 7.5 540 7 Colorless Tasteless Odorless 25 1.3 7.5 560 8 Colorless Tasteless Odorless 29 0.8 7.4 513 9 Colorless Tasteless Odorless 28 1.0 7.9 695 10 Colorless Tasteless Odorless 30 1.2 7.2 715 11 Colorless Tasteless Odorless 30 1.2 7.5 735 12 Colorless Tasteless Odorless 31 1.5 7.4 750 13 Colorless Tasteless Odorless 28 2.0 7.5 640 14 Colorless Tasteless Odorless 28 1.8 7.2 671 15 Colorless Tasteless Odorless 27 1.7 7.3 640 Temp. = Temperature NU = Natural Unit of Turbidity TH = Total Hardness Turb. = Turbidity CaH = Calcium Hardness MgH = Magnesium Hardness Table 3: physical and chemical parameters of ground water samples for wells under consideration Concentrations of chemical parameters (mg L-1) 2+ 2+ + + Well Ca HCO3CO32NO3Mg Na K ClSO42(NO.) 1 88 39.2 60 8 90 60 330 0.310 0.01 2 104 41.65 100 12 80 50 420 0.394 0.05 3 76 41.6 40 6 60 40 350 0.329 0.10 4 44 41.6 60 8 32 10 220 0.206 0.03 5 52 41.6 100 14 80 04 260 0.244 0.018 6 60 41.6 112 18 70 80 270 0.253 0.07 7 76 34.3 120 24 100 96 300 0.282 0.10 8 52.8 28.9 60 12 60 80 240 0.225 0.02 9 68 31.85 72 20 80 100 320 3.00 0.04 10 72 41.6 40 10 100 80 330 0.310 0.08 11 84 41.6 48 12 110 40 370 0.347 0.08 12 84 41.6 52 16 100 60 340 0.319 0.06 13 72 19.6 44 8 60 60 360 0.338 0.20 14 80 36.75 52 12 80 80 300 0.282 0.100 15 72 25.97 36 6 72 80 350 0.320 0.15

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TDS mg L-1 520 602 488 302 356 374 386 357 467 480 491 500 434 452 434

TH mg L-1 380 430 360 280 300 320 330 250 300 350 380 380 260 350 286

CaH mg L-1 220 260 190 110 130 150 190 132 170 180 210 210 180 200 180

PO43-

Mn2+

Fe2+

SiO2

0.60 0.40 0.40 0.16 0.035 0.10 0.15 0.30 0.18 0.11 0.15 0.15 0.50 0.60 0.5

0.20 0.16 0.20 0.20 0.30 0.20 0.30 0.20 0.30 0.20 0.12 0.10 0.60 0.8 0.8

0.20 0.10 0.10 0.1 0.15 0.15 0.20 .08 0.10 0.10 0.05 0.08 0.60 0.80 0.60

23 25 25 15 18 15 16 20 18 20 18 18 30 28 25

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MH mg L-1 160 170 170 170 170 170 140 118 130 170 170 170 80 150 106

Table 4: Statistical summary of the Hydro geochemical parameters Parameters Min. Max. Mean EDWS Temp. 25 31 27.266 NS Turbidity 0.8 2.00 1.38 10 pH 7.2 7.9 7.4 6.5-9.2 EC(µs cm-1) 420 920 654.87 NS TDS (mg L-1) 302 602 442.87 1200 TH (mg L-1) 250 430 330.4 500 CaH (mg L-1) 110 260 180.8 NS MgH (mg L-1) 80 170 149.6 NS HCO3- (mg L-1) 220 420 317.33 NS CO32- (mg L−1) 0.206 3.00 0.477 NS Cl- (mg L-1) 32 110 78.266 500 SO42- (mg L-1) 4.00 100 61.33 400 Ca2+ (mg L-1) 44 104 72.32 200 Mg2+( mg L−1) 19.6 41.65 36.628 150 Na+( mg L−1) 36 120 66.4 200 K+ (mg L-1) 6.00 24 12.40 NS Fe2+ (mg L-1) 0.05 0.80 0.252 1.00 Mn2+ (mg L-1) 0.1 0.8 0.30 0.50 NO3- (mg L-1) 0.01 0.20 0.0738 44 PO43-(mg L-1) 0.035 0.60 0.289 NS SiO2 (mg L-1) 15 30 20.93 NS Max. = Maximum value Min = minimum value SD = Standard Deviation NS = Not stated EDWS = Egyptian drinking water standard

WHO NS NS 6.5-8.5 NS 500-1500 500 NS NS NS NS 250 250 NS 50 200 NS 0.30 0.100 44 NS NS

SD 1.98 0.3124 0.001 139.76 78.14 61.43 38.81 35.514 53.24 0.700 20.400 28.54 15.49 7.07 27.93 5.35 0.225 0.365 0.500 0.26 4.78

Table 5: Ground water classification based on total hardness (Sawyer and McCartly 1967). Total hardness as CaCO3(mg L-1) Classification <75 Soft 75-150 Moderately hard 150-300 Hard >300 Very hard Major ions constitute the most significant part of the total dissolved solids present in the groundwater and the concentration of these ions in groundwater depends mainly on the hydro chemical processes that take place in the aquifer system (Lakshmanen et al., 2003). Major ions in the groundwater present a definite spatial trend. The distributions of the ionic components of the groundwater in the study area are shown in Figures 3–11.

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Figure 3: Relationship between

Figure 4: Relationship between

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Figure 5: Relationship between

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3.2 Assessment of groundwater suitability for irrigation Electrical conductivity, total dissolved salts and Kelly index were used for the classification of water for irrigation purposes. 3.2.1 Electrical conductivity and total dissolved salts EC is a good measure of salinity hazard to crops. Excess salinity reduces the osmotic activity of plants and thus interferes with the absorption of water and nutrients from the soil (Saleh et al., 1999; Sreenivasa and Ajay Kumar, 2016). Table 6 showed that the electrical conductivity (EC) values are ranged between 420µs cm-1 for well (4) and 920 µs cm-1 for well (2) with mean value of 654.87 Table 6: Salinity hazard class (Wilcox, 1995). Water class EC (µmohs cm-1) C1 100 – 250 C2 250 – 750 C3 750 – 2250 C4 and C5 >2250

Remark on quality Excellent Good Doubtful Unsuitable

3.2.2 Kelly index Sodium measured against calcium and magnesium was considered for calculating Kelly index (Kelly, 1951) by using the formula: KI = Where, all the ions are expressed in meq L-1(Table 6). The KI values of the study area were ranged from 0.230 to 0.815 meq L-1 with mean of 0.527 meq L-1. According to Table 7, all the values of KI for wells under consideration are below one; hence water is suitable for irrigational practice. Ph ton

µScm-1. The increase of EC value mainly related to the effect of pollution; which increases the concentrations (Masoud et al., 2003) ofCa2+, Mg2+, HCO3- and Cl-. According to table 5, the EC values are within the range of good quality to doubtful water for irrigational practice (Wilcox, 1995). Majority of the wells under consideration are characterized by good water quality, while wells (1and 2) revealed doubtful quality water for irrigational Practice. Total dissolved salts (TDS) values are ranging from 302mg L-1 to 602mg L-1 in for wells number 4 and 2 respectively with mean of 442.87 mg L-1. All the values are less than 1000 mg L-1, and hence are within the non-saline class (Fetter, 1990).

4. Groundwater classifications in study area 4.1 Groundwater classifications according to its relative content of cations and anions According to figure12 (Water type of the ground water in the western Nile Delta based On Bazilevich and Pankova (1968) classification), in the eastern part, Mg–Na, Na–Ca and Ca–Na are the predominant cations due to the cation exchange

313

HCO3-and HCO3- – Cl- (Figure 12) due to recharging from the River Nile, irrigation canals (Nubaria, Bustan) and excess irrigated water. In the western area the predominant anions areSO42- – Cland HCO3- – Cl- due to mixing of water from the Moghra aquifer and the Quaternary aquifer. In the northern part, the predominant anion is Cl-due to seawater intrusion.

with clays that are included in the Pleistocene aquifer. In the southwestern part, Mg–Na and Na are the predominant cations because Miocene aquifer affects the Quaternary aquifer through mixing between marine water and meteoric water. In the northern area, the predominant cations are Mg–Na due to the presence of saline water from the local lakes and the Mediterranean Sea. The predominant anions in the eastern area are Cl- –

Table 7: concentrations of major ions in meq L-1 and Kelly index for wells under consideration (meq L-1% Well No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Ca

2+

4.4 5.2 3.8 2.2 2.6 3.00 3.8 2.64 3.4 3.6 4.2 4.2 3.6 4.00 3.6

Mg

2+

3.27 3.47 3.46 3.47 3.47 3.47 2.59 2.40 2.65 3.46 3.46 3.46 1.63 3.06 2.16

Na

+

2.60 4.34 1.74 2.60 4.34 4.87 5.21 2.60 3.13 1.74 2.08 2.26 1.91 2.26 1.56

+

Sum.

Cl

0.21 0.315 0.157 0.21 0.368 0.473 0.631 0.315 0.526 0.263 0.315 0.421 0.210 0.315 0.157

10.48 11.48 9.157 8.48 10.778 11.813 12.23 7.955 10.916 9.063 10.055 10.44 7.35 9.635 7.477

2.54 2.25 1.69 0.90 2.25 1.97 2.82 1.70 2.25 2.82 3.10 2.82 1.70 2.25 2.03

K

-

SO4

2-

1.25 1.04 0.83 0.20 0.083 1.66 2.00 1.66 2.08 1.66 0.833 1.25 1.25 1.66 1.66

HCO3

-

5.41 6.88 5.74 3.60 4.26 4.43 4.92 3.93 5.24 5.41 6.07 5.57 5.90 4.91 5.73

2-

Sum.

0.010 0.013 0.011 0.007 0.008 0.008 0.010 0.007 0.10 0.01 0.011 0.01 0.011 0.010 0.010

9.21 10.18 8.271 4.707 6.601 8.068 9.75 7.297 9.67 9.90 10.01 9.65 8.861 8.83 9.430

CO3

Kelly Index 0.338 0.500 0.239 0.458 0.714 0.752 0.815 0.515 0.517 0.246 0.271 0.295 0.365 0.320 0.270

Figure 12: Water type of the ground water in the western Nile Delta based On Bazilevich and Pankova (1968) classification: (A) Major cations and (B) Major anions.

The salt types are determined by calculating the cations and anions using the nomenclature given by Bazilevich and Pankova (1968) as shown in Table 8.

Ph ton

314

Table 8: Nomenclature of Anion and cation ratios (Bazileviech and Pankova1968 ). Mg2+/Ca2+ Na+/Ca2+ Na+/Mg2+ More than 2.5 More than 2.5 More than 1.00 More than 1.00 More than 1.00 Less than 1.00 More than 1.00 More than 1.00 More than 1.00 Less than 1.00 Less than 1.00 More than 1.00 More than 1.00 Less than 1.00 Less than 1.00 Less than 1.00 More than 1.00 Less than 1.00 Less than 1.00 Less than 1.00 More than 1.00 Less than 1.00 HCO3-/SO42HCO3-/ClCl-/ SO42More than 2.5 2.5 – 1.00 1.00 - 0.200 0.200 More than 1.00 Less than 1.00 More than 1.00 Less than 1.00 More than 1.00 Less than 1.00 More than 1.00 More than 1.00 More than 1.00 More than 1.00 More than 1.00 Less than 1.00 Tables (9 and 10) show nomenclature of anion and cation ratios in the study area.

Salt type Sodium Magnesium- Sodium Calcium - Sodium Calcium - Magnesium Sodium - Magnesium Sodium - Calcium Magnesium - Calcium Magnesium Salt type Chloride Sulfate- chloride Chloride - Sulfate Sulfate Hydrocarbonate -Chloride Hydrocarbonate -Sulfate Chloride - Hydrocarbonate Sulfate - Hydrocarbonate

Table 9: Nomenclature of cation ratios in study area using the nomenclature given by Bazilevich and Pankova (1968). Well Mg2+⁄ Na2+ Na2+ 2+ No Ca ⁄ ⁄ Salt type Ca2+ Mg2+ 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

0.734 0.667 1.436 1.577 1.334 1.156 0.667 0.909 0,779 0.961 0.823 0.823 0.377 0.765 0.600

0.590 0.834 0.457 1.181 1.669 1.623 1.371 0.984 1.276 0.483 0.495 0.538 0.530 0.565 0.433

0.794 1.250 0.502 0.749 1.250 1.403 2.008 1.083 1.637 0.502 0.601 0.653 1.165 0.738 0.740

Magnesium - Calcium Sodium – Calcium Calcium – Magnesium Sodium – Magnesium Magnesium- Sodium Magnesium- Sodium Calcium – Sodium Sodium – Calcium Calcium – Sodium Magnesium – Calcium Magnesium – Calcium Magnesium – Calcium Sodium – Calcium Magnesium – Calcium Magnesium – Calcium

Table 10: Nomenclature of Anion ratios in study area using the nomenclature given by Bazilevich and Pankova (1968). Well HCO3- HCO3Cl-⁄ No ⁄ ⁄ SO42Salt type 2SO4 Cl 1 4.341 2.160 2.000 Chloride - Hydrocarbonate 2 6.619 3.000 2.164 Chloride - Hydrocarbonate 3 6.923 3.352 3.034 Chloride - Hydrocarbonate 4 18.03 4.000 4.503 Chloride - Hydrocarbonate 5 51.63 1.852 27.28 Chloride - Hydrocarbonate 6 2.661 1.476 1.183 Chloride - Hydrocarbonate 7 2.450 1.744 1.410 Chloride - Hydrocarbonate 8 2.368 2.311 1.024 Chloride - Hydrocarbonate 9 2.519 2.328 1.084 Chloride - Hydrocarbonate 10 3.271 1.920 1.696 Chloride - Hydrocarbonate 11 7.286 1.958 3.721 Chloride - Hydrocarbonate

Ph ton

315

12 13 14 15

4.458 4.542 2.889 3.353

1.970 3.470 2.180 2.807

2.240 1.308 1.353 1.176

Chloride - Hydrocarbonate Chloride - Hydrocarbonate Chloride - Hydrocarbonate Chloride - Hydrocarbonate

4.2 Sulin’s Classification Sulin’s graph (1948) for genetic classification of groundwater was used to indicate the water genesis and water type using the Hydrochemical composition (Sulin, 1948) as in shown in Table 11 and Figurev13. Groundwater has been divided into four genetic types: 1. Sulfate-sodium type of meteoric water in origin and associated sulfates are derived from terrestrial conditions.

2. Bicarbonate-sodium type in which water reflects meteoric associations, and continental conditions for the bicarbonates. 3. Chloride-magnesium type in which water reflects marine environments and evaporates sequences. 4. Chloride-calcium type that is associated with subsurface water bodies that could be non-meteoric

Table 11: Types of water genetic classification according to the Sulin's system Type of water Na+/Cl(Na+ - Cl-)/SO42(Cl- - Na-)/Mg2+ Chloride – Calcium <1 <0 >1 Chloride – Magnesium <1 <0 <1 Sodium – bicarbonate >1 >1 <0 Sodium – Sulfate >1 <1 <0 Figure 13: Sulin's graph for genetic classification of the groundwater in the western

Ph ton

316

Hydro geochemical Facies Analysis and ionic ratios values of groundwater under consideration have been recorded in Table 12 (1-5). Table 12: Ionic ratios of the ground water in the study area + Na ( Cl Cl-⁄ Well Ca2+⁄ Na HCO3 2+ 2No Mg SO4 ⁄ ⁄ SO" 2+ 2Mg SO4 1 1.345 0.794 4.341 2.000 -0.174 2 1.499 1.250 6.619 2.164 1.537 3 0.696 0.502 6.923 3.034 -0.142 4 0.634 0.749 18.03 4.503 2.710 5 0.749 1.250 51.63 27.28 4.952 6 0.865 1.403 2.661 1.183 0.815 7 1.499 2.008 2.450 1.410 0.667 8 1.100 1.083 2.368 1.024 0.405 9 1.283 1.637 2.519 1.084 0.771 10 1.040 0.502 3.271 1.696 -0.544 11 1.215 0.601 7.286 3.721 -1.237 12 1.215 0.653 4.458 2.240 -0.553 13 2.652 1.165 4.542 1.308 0.450 14 1.307 0.738 2.889 1.353 -0.134 15 1.666 0.740 3.353 1.176 0.0033

Ph ton

Cl ( Na Mg 0.076 -0.520 0.037 -0.281 -0.192 -0.572 -0.645 -0.307 -0.680 0.264 0.299 0.214 -0.298 0.081 -0.002

Cl ( /Na 0 K % Mg -0.052 -0.608 -0.007 -0.341 -0.298 -0.709 -0.889 -0.437 -0.877 0.219 0.209 0.092 -0.417 -0.021 -0.077

317

4.3 Hydro geochemical facies classification The diagnostic chemical characters of water solutions in hydrologic systems has been determined with the application of the concept of hydro chemical facies (Back, 1966) which enables a convenient subdivision of water compositions by identifiable categories and reflects the effect of chemical processes occurring between the minerals within the subsurface rock units and the groundwater. Statistical distribution diagrams such as Piper trilinear (Piper, 1944) is used to gain better insight into the hydro chemical processes operating in the groundwater system. The Piper tri-linear diagram was used for the purpose of characterizing the water types present in the area. It permits the cation and anion compositions of many samples to be represented on a single graph in which major groupings or trends in the data can be discerned visually (Freeze and Cherry, 1979). Water types are often used in the characterization of waters as a diagnostic tool (Leybourne et al., 1998; Pitkanen et al., 2002).

The piper tri- linear diagram to identify the hydro chemical facies of the ground water wells under consideration is shown in Figure 14. For the cations, major portion of the water samples present in the Ca zone followed by Na – K zone while for the anions, HCO3- is dominant. The diamond diagram shows that water of wells under consideration is of Ca– HCO3-for wells (3, 4, 5, 8, 9, 10, 11,12, 13, 14, and 15)followed by mixed Ca– Na–HCO3-in wells (2,6, and 7) and Ca–Cl of well (1). Thus Ca– HCO3-type is dominant. Ca– HCO3type is typical of shallow fresh ground waters, Na– HCO3-waters are characteristics of deeper ground waters influenced by ion exchange. The classic bibliography on ion exchange processes in coastal (Howard and Lloyd, 1983; Tellam and Lloyd, 1986; Lioyd and Tellam, 1988; Ikeda, 1989; Appelo and Postma, 1993) aquifers state that the appearance of Ca–Cl facies in a coastal aquifer reflects the operation of inverse ion exchange, whereas the Na–HCO3-facies can indicate direct exchange. The predominance of Ca–Cl or Ca–Cl, SO42- facies over much of the aquifer clearly indicates the existence of inverse ion exchange.

Figure 14:Piper trilinear diagrams for facies classification

5. Ionic ratios During rock weathering, Ca2+, Mg2+, SO42-, HCO3-, and SiO2are added to water. The amount of each ion in water is dependent on the rock mineralogy. However, the use of major ions chemistry to identify rock mineralogy can be useful but must be applied carefully. Mineral precipitation, ion exchange and evaporation can modify chemical composition. In many cases, the source rock minerals may be deduced from the water composition. Ph ton

Ionic ratios of ground waters have been often used to evaluate seawater intrusion in coastal areas Sanchez-Martos et al., 2002; Kim et al., 2003; Moujabber et al., 2006).The values ofHCO3-/ Cl-, indicative of freshwater recharge are all greater. Generally, the ratios gradually increase and approach the seawater value as TDS increases, indicating increase in influence of seawater intrusion.

318

Using ionic ratios in groundwater, it is possible to indicate the minerals of source rock types(Hounslow, 1995). For this purpose, the concentrations of the various constituents are converted to meq L-1to be able to combine the various ions in a chemically meaningful way. The ratio value of HCO3- / Cl-can be used as a good indicator for salinization due to the seawater encroachment. The value of HCO3- / Cl-ratioin this study is ranged between 1.47 and 4 as in Table 8. The results for theSO42-/ Cl-ratio and the calcium and magnesium concentrations are consistent with intrusion of seawater into the shallow aquifers. Ratios of Na/Ca, indicating cation exchange reaction can show some mixed behavior but it mostly increases with increase in TDS, which is a good indicator in revealing the salinization process (Edet and Okereke, 2002). Generally, some ionic ratios appeared useful to delineate degree of salinization effect for the ground waters. The ratios between ions (expressed in meq L-1) are shown in Table 14 (2-5). The Ca2++ Mg2+/total Cation ratio ranges from 0.522 to 0.792 while that for Na+ +K+/total Cation ranges from 0.207 to 0.477 as shown in Table 14. These values reflect the contribution of alkalis to total Cations. Water having Na+ +K+/total Cation ratio equal or higher than 0.5 indicate the contribution of cations via silicate weathering(MatiniL. et al., 2012). All the wells under consideration have Na+ +K+/total Cation ratio less than 0.5, thus there is no contribution of cations via silicate weathering. The water–rock interaction was exemplified by plotting some relation between major ions. The Ca2+/Mg2+ ratio ranged from 0.634 to 2.652. Ratio values higher than 1 indicate the predominance of Ca2+ over Mg2+ while low values indicate low residence time of water in the aquifer thereby signaling less weathering process. The Na+/Cl- ratios were ranged from 0.62 to 2.90 as shown in Table 15. The Na+/ Cl- ratios have been computed to determine the reasons of salinity in the groundwater. A Na+/Clratio equal to 1 indicates the dissolution of NaCl while a ratio greater than 1 indicates the release of Na+ from silicate weathering (Meybeck, 1987). Wells numbers 1, 3 and 14 have Na+/ Cl- ratio equal to one, while that for wells (2,4,5,6,7,8, 9 and 13) is higher than one. To determine the possibility of ion exchange as a source of Na in the ground water, both the Na+/Ca2+ and Na+/Na++Clratios were + 2+ determined.Na /Ca ratio for wells under consideration were ranged from 0.433 to 1.669 as shown Table 16, while the range of Na+/Na++Clwas from 0.381 to0.742. Ion exchange process as a source of Na+ can thus be highlighted in the groundwater chemistry mechanism. Ph ton

Changes in chemical composition of groundwater along its flow path can be understood by studying the Chloro-Alkaline Indices (CAI). (Schoeller, 1965; Schoeller, 1977) suggested two ChloroAlkaline Indices (CAI1,2) for the interpretation of ion exchange between groundwater and host environment. The Chloro-Alkaline Indices are calculated from the following relations: 1) Chloro-Alkaline Indices (CAI 1) = [Cl – (Na+ + K+)]/Cl2) Chloro-Alkaline Indices (CAI 2) = [Cl- – (Na+ + K+)]/SO42-+HCO3-+ CO32+NO3Positive Chloro-Alkaline Indices indicate exchange of Na and K from the water with Mg and Ca of the rocks and is negative when there is an exchange of Mg and Ca of the water with Na and K of the rocks (Nagaraju et al., 2006). In this present study, CAI1 values range from -1.7 to 0.980 with mean of 0.360 while CAI2 values range from -0.415 to 0.143 with mean value of -0.136 table9.5. All the wells under consideration are recorded negative values of CAI except wells (10, 11, 12, and 15) which have positive values. This means that there is an exchange of Mg and Ca of the water with Na and K of the rocks in wells(1, 2, 3, 4, 5, 6, 7, 8, 9, 13, and 14) while there is exchange of Na and K from water with Mg and Ca of the rocks in wells numbers 10, 11, 12, and 15. Silicate and carbonate weathering can be ascertained from the HCO3-/Na+ ratios (Matini et al., 2012). A ratio greater than one indicates carbonate weathering while a ratio less than one implies silicate weathering. The ratio in the water samples of the wells under consideration ranged from 0.909 to 3.673, thereby showing both silicate and carbonate weathering to be the dominant weathering process. In all the water samples of the wells under consideration, the concentration of Na+ is greater than that of K+ as the latter is more resistant to chemical weathering and its adsorption on the clay materials. The value of the HCO3+SO42- / total anion ratios ranged from 0.658 to 0.808, and as the ratio is less than one, it can be seen that there is a deficiency ofHCO3- and SO42ions in the groundwater. This implies that there is less effect of rain in the rock-water interaction. This is additionally supported by the low range (<1) of Cl-/total Anion ratio values (0.191 to 0.478).

319

Table 14: Ionic ratios of the ground water in the study area Well No. (Ca2++Mg2+)/T.cations (Na++K+)/T.cations 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 T = total

0.731 0.755 0.792 0.668 0.563 0.548 0.522 0.633 0.554 0.779 0.761 0.733 0.711 0.733 0.77

0.268 0.405 0.207 0.331 0.436 0.452 0.477 0.366 0.335 0.220 0.238 0.256 0.288 0.267 0.229

HCO3-/ T.anions

Cl-/T.anions

0.587 0.675 0.694 0.765 0.645 0.549 0.504 0.538 0.541 0.546 0.606 0.577 0.665 0.556 0.607

0.275 0.221 0.204 0.191 0.478 0.244 0.289 0.232 0.232 0.284 0.309 0.292 0.191 0.254 0.215

Table 15: Ionic ratios of the ground water in the study area Well Na+/Na++ClHCO3-/Na+ Cl-/ HCO3No. 1 0.505 2.080 0.469 2 0.658 1.585 0.327 3 0.507 3.298 0.294 4 0.742 1.384 0.250 5 0.658 0.981 0.528 6 0.711 0.909 0.444 7 0.648 0.944 0.717 8 0.604 1.511 0.432 9 0.581 1.674 0.429 10 0.381 3.109 0.521 11 0.401 2.918 0.510 12 0.444 2.464 0.506 13 0.529 3.089 0.288 14 0.501 2.172 0.458 15 0.434 3.673 0.354

Ph ton

HCO3-+ /T.anions 0.723 0.775 0.794 0.808 0.658 0.754 0.709 0.766 0.756 0.714 0.689 0.706 0.806 0.744 0.783

SO42-

HCO3-/ T.cation 0.516 0.599 0.626 0.424 0.395 0.375 0.402 0.494 0.480 0.597 0.603 0.533 0.802 0.508 0.766

320

Table 16: Ionic ratios and chloro alkaline indices of the ground water in the study area W Na+ Mg2+ Na+⁄ Ca2+ Mg+ K+⁄ Ca2+ Ca2+ ell ⁄ ⁄ Cl ⁄ ⁄ Cl ⁄ ⁄ No Ca2+ Ca2+ ClClSO42HCO3. 1 0.590 0.743 1.00 1.73 1.28 0.08 2.97 0.813 2 0.834 0.667 1.72 2.31 1.54 0.14 4.43 0.755 3 0.457 0.910 1.00 2.24 2.05 0.09 4.13 0.662 4 1.181 1.577 1.60 2.44 3.90 0.23 6.10 0.330 5 1.669 1.334 1.18 1.15 1.54 0.16 19.3 0.370 6 1.623 1.156 1.68 1.52 1.76 0.24 1.23 0.460 7 1.371 0.667 1.47 1.34 0.91 0.22 1.51 0.610 8 0.984 0.909 1.39 1.55 1.41 0.19 1.42 0.600 9 1.276 0.779 1.72 1.51 1.17 0.23 1.45 0.570 10 0.483 0.961 0.62 1.27 1.23 0.09 2.38 0.730 11 0.495 0.823 0.67 1.35 1.12 0.10 5.02 0.680 12 0.538 0.823 0.80 1.49 1.23 0.15 3.13 0.700 13 0.530 0.377 1.30 2.11 0.96 0.12 3.33 0.730 14 0.565 0.765 1.00 1.80 1.36 0.14 2.16 0.740 15 0.433 0.600 1.00 1.77 1.20 0.08 2.65 0.790

Conclusion The results give the abundance of the cations in the following order: Ca2+> Na+> Mg2+ > K+, while those of the anions were in the following order: HCO3-> Cl- > SO42- > CO32- > PO43-> NO3-.

HCO3⁄ Cl-

SO42-⁄ Cl-

Chloro Indices

Alkaline

2.160 3.000 3.352 4.000 1.852 1.476 1.744 2.311 2.328 1.920 1.958 1.970 3.470 2.180 2.807

0.520 0.462 0.488 0.222 0.035 0.842 0.714 0.976 0.924 0.592 0.267 0.446 0.764 0.737 0.817

1 -0.106 -1.062 -0.105 -1.911 -1.084 -1.700 -3.010 -1.200 -1.390 0.820 0.980 0.130 -0.235 -o.310 0.310

2 -0.033 -0.234 -0.021 -0.404 -0.369 -0.415 -0.308 -0.164 0.143 0.082 0.070 0.013 -0.046 -0.035 0.032

All the wells under consideration are recorded negative values of CAI this means that there is an exchange of Mg and Ca of the water with Na and K of the rocks in these wells, while there is exchange of Na and K from water with Mg and Ca of the rocks in some wells. Research Highlights

The concentrations of all parameters for all wells are below than the recommended levels except wells numbers 13, 14 and 15 which are with Mn and iron contents greater than the recommended level.

This research successfully concerned with Evaluation of ground water in Kom Hamada city, Southern Egypt.

Kelly index values for all wells under consideration are below one; hence waters are suitable for irrigational practice.

Physico-chemical parameters of different wells at different zones were analyzed.

The hydro chemical composition reflects the Na2SO4 water type, indicating the old meteoric genesis. All the wells under consideration have Na+ +K+/ total Cation ratio less than 0.5, thus there is no contribution of cations via silicate weathering.

The values of all parameters for wells under consideration are less than the maximum permissible limits except some wells.

Ph ton

321

Owing to the hydro geological heterogeneity hydro chemical characteristics were evaluated. The ionic interactions as well as the hydro geochemical facies distribution in the area had been done. Limitations It is important to mention here that; no governmental or any scientific limitations to influence the interpretation of Results and Conclusion

Back W., 1966. Hydro chemical facies and groundwater flow patterns in northern part of Atlantic Coastal Plain: US Geological Survey Professional Paper 498 – A, 42. Bazilevich N.I., Pankova E.I., 1968. A Tentative of classifying soils according to salinization, Pachvavedena 11: 3-16 Bodek I., Lyman W. J., Reehi W. F., Rosenblatt D.H., 1988. Environmental, Inorganic Chemistry: properties, processes and estimation methods. Pergamon Press, New York

Recommendation

Burkart M.R., Stoner J.D., 2002. Nitrate in aquifers beneath agricultural systems, Water Science and Technology 45(9), 19–29

It is strongly recommended research required to find new underground water resources as an alternative of limited River Nile source to overcome problem of increasing population rate in Egypt.

Carpenter S.R., Caraco N.F., Correll D.L., Howarth R.W., Sharpley A.N., Smith V.H., 1998. Nonpoint pollution of surface waters with phosphorus and nitrogen, Ecological Applications 8(3), 559–568

Acknowledgments

Chaudhuri S., Ale S., 2014. Long term (1960–2010) trends in groundwater contamination and salinization in the Ogallala aquifer in Texas. J. Hydrol. 513(26), 376–390

It important to acknowledge facilities of chemicals, collection of samples personnel, field lab measurements, finance support given by El-Behera governorate, Cairo University and Madina Higher Institute of Engineering. Authors’ Contribution and Competing Interests The authors are in team work as supervisor professor M.A. Zayed working with his Ph.D. student Adel Elhdad water research field aiming to find new underground water resources as an alternative of limited River Nile source to overcome problem of increasing population rate in Egypt. References Abdel Moati M.A.R., 1985. "Study on the chemical of lakeManzalah waters" Ph.D. Thesis, Faculty of Science, Alexandria Univ., Egypt. 433 P Ahmed M.A., Abdel Samie S.G., Badawy H.A., 2013. Factors controlling mechanisms of groundwater salinization and hydrogeochemical processes in the Quaternary aquifer of the Eastern Nile Delta, Egypt Environ. Earth Sci. 68(2), 369–394. American Public Health Association (APHA), 2012.Standard Methods for examination of water, and waste water, 22nd Edn.APHA, AWWA, WPCF, Washington DC, USA. 1360 pp. ISBN 978-087553-013-0. Appelo C.A.J., Postma D., 1993.Geochemistry, groundwater and Pollution. Balkema, Rottadam, NL, 530 536

Ph ton

Chebbah M., Allia Z., 2015. Geochemistry and hydrogeochemical process of ground water in the Souf Valley of low septentrional Sahara, Algeria, African Journal of Environmental Science and Technology Vol. 9(3). PP. 261-273 Choi W.-J., Han G.-H., Lee S.-M., Lee G.-T., Yoon K.-S., Choi S.-M.I, Ro H.-M., 2007. Impact of land-use types on nitrate concentration and δ 15N in unconfined groundwater in rural areas of Korea. Agriculture, Ecosystems and Environment 120(2 – 4), 259–268 Cloutier V., Lefebvre R., Therrien R., Savard M.M.,2008.Multivariate statistical analysis of geochemical data as indicative of the hydrogeochemical evolution of groundwater in a sedimentary rock aquifer system. Journal of Hydrology 353(3), 294-313. Cruz J.V., Coutinho R., Pacheco D., Cymbron R., Antunes P., Freire P., Mendes S., 2010. Groundwater salinization in the Azores archipelago (Portugal). Environ. Earth Sci. 62(6), 1273–1285 Dawoud M.A., Darwish M.M., EL-Kady M.M., 2005. GISbased groundwater management model for western Nile Delta, Water Resources Management 19 (5): 585–604 Davis S.N., 1964. Silica in streams and ground water. American Journal of Science 262(7), 870–891 Das A., Bandopadhyay D. K., Jee P. K., and Chowdhury I. R., 2015.Hydrogeochemistry of groundwater in chandanpur area of Odisha, India, Intrnational Journal Of Geomatics And Geosciences Volume 5, No 3, pp. 448-458.

322

Edet A.E., Okereke C.S., 2002. Delineation of shallow groundwater aquifers in the coastal plain sands of Calabar area (Southern Nigeria) using surface resistivity and hydro geological data, Journal of African Earth Sciences35(3), 433-443. Edmunds W.M., Ma J.Z., Aeschbach-Hertig W., Kipfer R., Darbyshire D.P.F., 2006. Groundwater recharge history and hydrogeochemical evolution in the Minqin Basin, North West China, Applied Geochemistry 21(12), 2148–2170. Edmunds W.M., Gaye C.B., 1997. Naturally high nitrate concentrations in groundwater's from the Sahel, Journal of Environmental Quality 26(5), 1231- 1239. Egyptian Ministry of Health and Population, 2007.Standards and specifications of water Quality for drinking and domestic uses. Internal report: 8,

and GIS mapping in Jada area, Northeastern Nigeria. Journal of Earth Sciences and Geotechnical Engineering vol. 1, no. 1, 35-60. Kelly W.P., 1951. Alkali Soils-Their Formation, properties and Reclamation.3rd edition. Reinhold Publ., New York, USA. 92. Kim J.H, Kim R.H., Chang H.W., (2003). Hydro geochemical Characterization of major factors affecting the quality of shallow Groundwater in the coastal area at Kimje in South Korea, Environmental Geology 44(4), 478- 489 Knee K.L., Layton B.A., Street J.H., Boehm A.B., Paytan A., 2008. Sources of nutrients and fecal indicator bacteria to nearshore waters on the north shore of Kaua’i (Hawai’i, USA), Estuaries and Coasts 31(4), 607–622.

El Abd E.A., 2005.The geological impact on the water bearing formations in the area southwest Nile Delta, Egypt. Unpublished Ph.D. Thesis, Fac. Sci., Menufiya Univ., Egypt, 319 p.

Knee K.L., A. Paytan, 2011. Submarine Groundwater Discharge: A Source of Nutrients, Metals, and Pollutants to the Coastal Ocean. In: Wolanski E and McLusky DS (eds.) Treatise on Estuarine and Coastal Science Vol 4, pp. 205– 233.

El Hdad A.M.A., 2006. Study on physicochemical changes and water treatment for Kom Hamada sector – El- beheira governor, Egypt. Ph.D. Thesis, Fac. Sci., Alexandria Univ., Egypt, 241p

Klinchuch A.L., Defino A.T., 2000. Reductive Dissolution and Precipitation of Manganese Associated with biodegradation of petroleum hydrocarbons, J. Environmental Geosciences. 7(2), 69-79.

Fetter C.W., 1990. Applied Hydrogeology. 2nd ed., CBS Publishers and Distributors, New Delhi, India, P 592

Lakshmanen E., Kannan R., Kumar M.S., 2003. Major ion chemistry and identification of hydrochemical processes of groundwater in a part of Kancheepuram District, Tamil Nadu, India, Environmental Geosciences 10(4), 157–166.

Freeze R.A., Cherry J. A., 1979. Ground water, PrenticeHall In. Englewood Cliffs, New jersey, 604PP. Gardner K.K., Vogel R.M., 2005. Predicting ground water nitrate concentration from land use, Ground Water 43(3), 343–352. Guo H., Yang S., Tang X.Li. Y., Shen Z., 2008. Groundwater geochemistry and its implications for arsenic mobilization in shallow aquifers of the Hetao Basin, Inner Mongolia, Sci. Total Environ. 393(1), 131–144. Haines T.S., Lloyd J.W., 1985. Controls on silica in groundwater environments in the United Kingdom.Journal of Hydrology. 81(3), 277–295. Hounslow A.W., 1995. Water quality data: analysis and interpretation, CRC Lewis Publishers, Boca Raton, FL, 10, pp. 86-87. Howard K.W.F, Lloyd J.W., 1983. Major ion characterization of coastal saline ground waters, Groundwater 21(4), 429-437. Ikeda K., 1989. Chemical evolution of groundwater quality in the southern foot of Mount Fuji, Bull. Geol. Surv. Japan 40 (7), 331- 404. Ishaku J.M.I., Ahmed A.S., Abubakar M.A., 2011. Assessment of groundwater quality using chemical indices Ph ton

Lawrence A.R., GoodyD.C., KanatharanaP.,MeesilpM.,RamnarongV.,2000. Groundwater evolution beneath Hat Yai, a rapidly developing city in Thailand, Hydrology Journal 8(5), 564– 575. Leybourne M.I., Good fellow W.D., Boyle D.R., 1998. Hydro geochemical, isotopic and rare earth element evidencefor contrasting water-rock interactions at two undisturbed Zn-Pb massive sulphide deposits, Bathurst Mining Camp, N.B, Canada, Journal of Geochemical Exploration, 64(1), 237-261. Lioyd J.W., Tellam J.H., 1988. Caraterizacionhidroquimica de las agues subterraneas en areas costeras (Hydro chemical characterization of groundwater in coastal areas), Proceedings of International Symposium TIAC’88 (Tecnologia de la Intrusion marina en AcuiferosCosteros), Vol. 1, Almunnecar, Granada, Spain, June 1-8. Matini L., Tathy C., Mouton J.M., 2012. Seasonal groundwater quality variation in Brazzaville, Congo. Research Journal of Chemical Sciences 2(1), PP 7-14. Masoud M.S., Zayed M. A., El Hdad A.M. A., 2003. Study of ground water quality in Kom Hamada area, Behira

323

Governorate, Egypt" Journal of Bulletin of the Chemists and Technology of Macedonia 22(2), PP. 143-154. Meybeck M., 1987. Global chemical weathering of surficial rocks estimated from river dissolved loads. American Journal of Science, 287(5), pp 401-428. Mohamed S.M., EL-Bady, 2014, Spatial Distribution of some Important Heavy Metals in the Soils South of Manzala Lake in Bahr El-Baqar Region, Egypt, Nova Journal of Engineering and Applied Sciences, Vol. 3(2), 112. MoujabberE.l.,Bou Samra M., Darwish B., Atallah T., 2006. Comparison of different indicators for groundwater contamination by seawater intrusion on the Lebanese Coast, Water Resources Management 20(2), 161 -180 Mtoni Y., Mjemah I.C., Bakundukize C., van Camp M., Martens K., Walraevens K. 2013. Saltwater intrusion and nitrate pollution in the coastal aquifer of Dares Salaam, Tanzania. Environ. Earth Sci. 70(3), 1091–1111. Mudiam M.K., Pathak S.P., Gopal K., Murthy R.C., 2012. Studies on urban drinking water quality in a tropical zone. Environ. Monit. Assess 184(1), 461–469. Mueller D.K., Helsel D.R., Kidd M.A., 1996. Nutrients in the Nation’s Waters: Too Much of a Good Thing? US Geological Survey Circular 1136. US Geological Survey, Denver, CO, 24 pp Nagaraju A., Suresh S., Killham K., Hudson-Edwards K., 2006. Hydrogeochemistry of Waters of Mangampeta Barite Mining Area, Cuddapah Basin, Andhra Pradesh, India.Turkish J. Eng. Env.Sci. 30 (4), 203-219. Nolan B.T., 2001. Relating nitrogen sources and aquifer susceptibility to nitrate in shallow ground waters of the United States, Ground Water 39(2), 290–299. Nouri J., Mahvi A.H., Jahed G.R., Babaei A.A., 2008. Regional distribution pattern of groundwater heavy metals resulting from agricultural activities, Environ. Geol. 55(6), 1337–1343. Nwankwoala H.O., Udom G.J., 2011. Hydrochemical Facies and Ionic Ratios of Groundwater in Port Harcourt, Southern Nigeria, Research Journal of Chemical Sciences 1(3), 97-101. Obiefuna G.I., Sheriff A., 2011.Assessment of Shallow Ground Water Quality of Pindiga Area, Yola Area, NE, Nigeria for Irrigation and Domestic Purposes. Research Journal of Environmental and Earth Sciences 3 (2): 131141. Oberdorfer J.A., Valentino M.A., Smith S.V., 1990. Groundwater contribution to the nutrient budget of Tomales Bay, California. Biodegradation 10, 199–216

Ph ton

Olayinka A. I., Abiombola A. F., ISibor R. A., Rafiu A. B., 1999. "A geoelectric Hydrochemical Investigation of Shallow ground water occurrence in Ibadam, southwestern Nigeria," Environmental Geology vol. 37, (1-2), pp. 31 – 37. Orajaka S., 1972. Salt water resource of East Central State of Nigeria, journal Min. Geol., In Geology of Neigeria, C.A. Kogbe (ed). Eliz Pub. Co. PP. 455-477. Peaslee D.E., Phillips R.E., 1981. Phosphorus dissolutiondesorption in relation to bioavailability and environmental pollution [soil]. In: Chemistry in the Soil Environment, Proceedings of a Symposium Sponsored by Division S-2 of the American Society of Agronomy and the Soil Science Society of America-Madison, Wis (USA: Published by the American Society of Agronomy, Soil Science Society of America pp. 241–259. Pitkanen P., Kaija J., Blomqvist R., Smellie J.A.T., Frape S.K., Laaksoharju M., Negral P.H., Casanova J., Karhu J., 2002. Hydro geochemical interpretation of groundwater at Palmottu, Paper EUR 19118 EN, European Commission, Brussels, 155 – 167. Pichiah S., Senthil Kumar G.F., Srinivasamoorthy K., Sarma V. S., 2013. Hydrochemical characterization and quality assessment of groundwater in TirupurTaluk, Tamil Nadu, India: Emphasis on irrigation quality J. Acad. Indus. Res. Vol.1(12), 805-812. Piper A.M., 1944. A graphical interpretation of water analysis, Transactions of the American Geophysical Union 25, 914 -928. Pradhan J.K., Kumar S., 2014. Informal e-waste recycling: Environmental risk assessment of heavy metal contamination in Mandoli industrial area, Delhi, India. Environ. Sci. Pollut. Res. Int. 21(13), 7913–7928. Prasanna M.V., Chidambaram S., Srinivasamoorthy K., 2010. Statistical analysis of the hydrogeochemical evolution of groundwater in hard and sedimentary aquifers system of Gadilam river basin, South India. Journal of King Saud University (Science) 22(3), 133-145. Saleh A., Al-Ruwaih F., Shehata M., 1999. Hydrogeochemical processes operating within the main aquifers of kuwait, J. Arid Environ 42(3), 195-209. Santhosh P., Revathi D., 2014.Geochemical Studies on the Quality of Ground Water in Tirupur District, Tamilnadu, India. Journal of Chemical, Biological and Physical Sciences 4(2), 1780-1786 Sanchez-Martos F., Pulido-Bosch A., Molina- Sanchez L., VallejosIzquierdo A., 2002.Identification of the origin of salinization in groundwater using minor ions (Lower ANDARAX, Southeast. Spain), Science of the Total Environment(29), 43-58.

324

Sawyer C. N., McCartly P. L., 1967. Chemistry for sanitary engineers.2nd edition. (New York McGraw Hill), 38, p. 3899 – 3908. Schoeller H., 1965. Qualitative evaluation of groundwater resources. In: Methods and techniques of groundwater investigations and development. Water resources series No. 33, UNESCO 54-83. Schoeller H., 1977. Geochemistry of groundwater. In: Brown RH etal (eds) groundwater studies- an international guide for research and practice. UNESCO, Parise, Ch.15, PP. 1-18. Seiler H.G., Sigel H., Sigel A., 1988. Hand Book on Toxicity of Inorganic Compounds, Marceel Dekker, Inc., New York p. 622. Shah B.A., 2013. Arsenic in groundwater, Quaternary sediments, and suspended river sediments from the Middle Gangetic Plain, India: Distribution, field relations, and geomorphological setting, Arab. J. Geosci. 7(9), 3525– 3536. Sharaky A.M., Atta S. A., El Hassanein A.S., Khallaf K. M. A, 2007. 2nd International Conference on the Geology of Tethys, 19-21 March, Cairo University, Hydrogeochemistry of Groundwater in the Western Nile Delta Aquifers, Egypt 1-23.

Tellam J.H., Lloyd J.W., 1986. Problems in the recognition of seawater intrusion by chemical means: an example of apparent chemical equivalence, Q. J. Eng. Geol., (19), 389398. Trabelsi R., Zairi M., Dhia H.B., 2007. Groundwater salinization of the Sfax superficial aquifer, Tunisia,Hydrogeol J. 15(7), 1341–1355. Triki I., Trabelsi N., Zairi M., Dhia H.B., 2014. Multivariate statistical and geostatistical techniques for assessing groundwater salinization in Sfax, a coastal region of eastern Tunisia. Desalin, water treat. 52(10-12), 1980– 1989. Wakida F.T., Lerner D.N., 2005. Non-agricultural sources of groundwater nitrate: a review and case study, Water Research 39(1), 3–16. WarldHealhOrgnization, Geneva, 1993. Guidline for Drinking Water Quality, 2ndedn, 1, 40. Wilcox L.V., 1995. Classification and Use of Irrigation Water, US Department of Agriculture Circular.969, Washington DC. US Department of Agriculture, P.19. Wong J.W.C., Chan C.W.Y., Cheung K.C., 1998. Nitrogen and phosphorus leaching from fertilizer applied on golf course: lysimeter study, Water, Air, and Soil Pollution 107(1), 335–345.

Sirajudeen J., Kahar Mohidheen M., Abdul Vahith R., 2014. Physico-chemical contamination of ground water in and around Tirunelveli district, Tamil Nadu, Pelagia Research library Advances in. Appl. Sci. Res. 5(2): 49-54.

World Health Organization, 2011.Guidelines for drinking water quality, v. 1, Recommendations, 4thEd.WHO, Geneva, Switzerland, 541.

Spalding R.F., Exner M.E., 1993. Occurrence of nitrate in groundwater – a review, Journal of Environmental Quality 22(3), 392–402.

World Health Organization, 2008. Geneva, guidelines for drinking-water quality [electronic resource]: incorporating 1st and 2nd addenda, v. 1, Recommendations, 3rdedn. 515.

Sreenivasa A., Ajay Kumar N. Asode, 2016, Study of Groundwater Quality using GIS in Hirehalla Sub-basin of Koppal District, Karnataka, India, International Journal of Advanced Earth Science and Engineering, 5(1), 364-374.

Younes S., 2012. Geochemical Evolution of Groundwater in MengXu Area, Gui Ping City, Southern China, Procedia Engineering 33(1), 340-350.

Srinivasamoorthy K., Gopinath M., Chidambaram S., Vasanthavigar M., Sarma V.S., 2014. Hydrochemical characterization and quality appraisal of groundwater from Pungar sub basin, Tamilnadu, India, Journal of King Saud University – Science 26 (1), 37-52.

Zayed M.A, El Hdad A.M.A, 2016. Assessment of selected physicochemical parameters to investigate the groundwater quality of El- Bheira Governorate, Egypt, European Academic Research 4(5), 4687- 4706.

Sulin V.A., 1948. Condition of formation, principals of classification and constituents of natural waters, Particularly Water of Petroleum Accumulation. Moscow. Leningrad, Acad. of Sc., USSR. Su A., Chen Z., Liu J., Wei W., 2014. Sustainability of intensively exploited aquifer systems in the North China Plain: Insights from multiple environmental tracers, J. Earth Sci. 25(3), 605–611.

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