Environ Earth Sci (2016) 75:746 DOI 10.1007/s12665-016-5441-8

ORIGINAL ARTICLE

Assessment of groundwater quality for irrigation and drinking purposes and identification of hydrogeochemical mechanisms evolution in Northeastern, Tunisia Faten Houatmia1 • Rim Azouzi1 • Abdelkrim Charef1 • Mourad Be´dir1

Received: 8 July 2015 / Accepted: 6 February 2016 Ó Springer-Verlag Berlin Heidelberg 2016

Abstract Oligocene and Mio-Plio-Quaternary siliciclastic deposits constitute the most important deep aquifers of the Kairouanai-Sahel region. Considering the over-exploitation and contamination of the surface groundwater, recourse to use deep groundwater was crucial. These aquifers revealed three major hydrochemical facies: HCO3/ Mg, HCO3/Na and SO4/Mg water types. Rock–water interaction showed the main mechanisms are rock weathering and evaporation. Different parameters such as water quality index (WQI), sodium absorption ratio (SAR), percentage of sodium, residual sodium carbonate (RSC), magnesium hazard (MH) and permeability index (PI) were used to evaluate groundwater suitability for drinking and irrigation purposes. Results highlighted that groundwater is unsafe for irrigation based on PI, MH, RSC and salinity diagram. According to the WQI values, 10.25 % of the water samples had good water quality, 69.23 % were considered as poor water, 12.82 % were very poor water and 7.69 % were considered unsuitable for drinking purpose. Keywords Physico-chemical analysis  Hydrogeochemistry  Drinking and irrigation quality  Sisseb El Alem aquifers

& Faten Houatmia [email protected] 1

Georesources Laboratory, CERTE-University Elmanar, BP-273, 8023 Soliman, Tunisia

Introduction In arid and semi-arid regions from North African countries, strategic plans depend on groundwater resources as rainfall is characterized by temporal and spatial variations that are random and sporadic. Consequently, to enhance water resources exploitation in these regions, it is important to understand the main process that controls groundwater mineralization (Bel Hadj Salem et al. 2014) to ensure safe use of the resources for drinking, agricultural and industrial purposes (Ben Alaya et al. 2014). In Tunisia, the hydrogeology is largely controlled by tectonic events, which created several multilayer deep aquifer systems (Lachaal et al. 2011, 2012; Gabtni et al. 2012; Houatmia et al. 2014). These most active faulting systems played a significant role in the lateral compartmentalization of hydrological reservoirs. To the Northeastern part of Tunisia, Sisseb El Alem basin characterized by agricultural activities with intensive application of pesticides and fertilizers and excessive groundwater abstraction led to the water contamination (Hamed et al. 2013) and the water resources deterioration. Groundwater has a unique chemistry due to several processes, such as general geology, degree of chemical weathering of a various rock types, rock–water interaction during recharge and ground water flow. Such factors and their interactions identify the geochemical properties and groundwater quality (Mathhess 1982; Kumar et al. 2007; Zahid et al. 2008; Gunduz et al. 2009; Mamatha and Rao 2009; Brindha and Elango 2012; Kraiem et al. 2013). In the study area, groundwater is used for both drinking and irrigation purposes (Kacem et al. 2008). Numerous publications have concentrated on groundwater quality monitoring and evaluated for domestic and agriculture activities. Laajili (2014) revealed nitrate and sulphate contamination of

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shallow groundwater and surface water attributed mainly to anthropogenic factors (agriculture and the use of treated wastewater) in Sisseb El Alem basin. In the present work, groundwaters from the Oligocene and Mio-Plio-Quaternary aquifers were characterized employing physico-chemical data to determine the water suitability for different uses (i.e., drinking and irrigation). This study was also designed for the hydrochemical characterization of these aquifer systems with the aim of orientation of the exploitation and protection of these important resources. The main objectives of this study are: (1) evaluation of water geochemistry, (2) determination of water quality parameters, and (3) assessment of water suitability for drinking and irrigation purposes by comparing various parameters: the water quality index (WQI), sodium percentage (% Na), sodium adsorption ratio (SAR), residual sodium carbonate (RSC), the Kelly’s ratio (KR), the permeability index (PI), and magnesium hazard (MH) with the standards and guidelines.

Geological and hydrogeological settings The Sisseb El Alem basin belongs to the northern Kairouan aquifer system, which is located in the northeastern part of Tunisia and extends over about 1064 km2. It is located between Draa Essouatir structure in the east, the Tunisian

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Atlassic Dorsal in the west, the Kairouan city in the south and the Nadhour-Saouaf region in the north (Fig. 1). This corresponds to the 3,940,000 and 4,000,000 north parallels and the 560,000 and 640,000 East meridians. It has an important tectonic activity which highlights the aquifers limits. The Sisseb El Alem plain has a semi-arid ‘‘Mediterranean’’ climate type characterized with dry and hot summer and wet and cool winter season. The mean annual rainfall and temperature are, respectively, about 252 mm and 20 °C and the potential evaporation for the period 2007–2011 has an average of 1500 mm/year. The important hydraugraphic netwok in the watershed consists of Nabhana, Khrioua and Ketem permanent rivers. There are many other temporary rivers (Essebkha, Dalloussi, Bouchkima, Elekhtifa, El Alem, BouAssane, El Terich and El Ogla). The Nabhanawadi is controlled by the Nebhana dam. Others wadis collects surface runoff from the surrounding hills. The main direction of this drainage network is from North–West to South–East (Kacem et al. 2008). The oldest sediment outcropping is the Triassic associate to the Zaghouan thrust (Turki 1985; Saadi 1997) to the northwest of the study area (Fig. 1a). The Oligocene and Mio-Pliocene series which outcrop in the surrounding anticlines of Edghafla, Bou Slem, Hmadet Essrassif, Sbikha and Draa Esssouatir are formed by sands and sandstones alternated with clays, marls and limestones. These

Fig. 1 Localization of: a Geological outcrops, sampled wells and b Rivers and Watershed limit

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series correspond to the Fortuna (Oligo-Aquitanian), AinGhrab (Lower to middle Langhian), Beglia (Upper Langhian-Serravalian), Souaf (Serravallian-Tortonian) and Segui (Tortonian-Lower Quaternary) Formations (Ellouze 1984; Be´dir 1985, 1988; Delteil and Turki 1986; Me´on and Tayech 1986; Turki 1985; Saadi 1992, 1997; Jeddi 1993; Yaich et al. 1994; Chihi 1995; Gaaloul 1995; Boujamaoui et al. 1997a; Yaich 1992, 1997; Boujamaoui and Inoubli 1999a, 1999b; Boujamaoui 2000; Be´dir et al. 2012; Khomsi et al. 2012). The Quaternary sedimentation is mainly constituted by thin terraces, soils, clays, sands, conglomerates and calcareous crusts which cover the entire Sisseb El Alem basin and lie unconformably over the Neocene series. Mineralogical analysis showed that the Oligocene and Miocene clay is mainly composed of different percentages of kaolinite (35, 34 %), respectively, illite (26, 15 %) and smectite (29, 39 %), respectively. Associated minerals are formed by quartz (10, 9), respectively, calcite (2, 0 %) and feldspar (1, 0 %), respectively (Jamoussi 2001). Oligocene and Mio-Plio-Quaternary deep groundwater constituted the main water resources in Northeastern Tunisia. These aquifers are intensively exploited during the last years due to the excessive demands of agricultural and demographic development. The exploited volume has an average of 9.18 in 2005 and 9.43 Mm3 in 2006 and raised to 9.51 Mm3 in 2011 (DGRE 2011) (Fig. 2). This overexploitation induced an important piezometric level decline (Fig. 2). The interpretation of the seismic data in terms of reservoir characterisations, as well as of the structural framework, highlights the different hydrogeological subbasins and the main potential fields for exploration-development of deep aquifers. The Draa Essouatir anticline is a positive flower structure limited by two thrust listric and deep faults (Fig. 3) ( Khomsi et al. 2004). It presents a hydrogeological barrier between two basins. These accidents have a synthetic–antithetic faults configuration. To the West, in Sisseb El Alem

Fig. 2 Deep groundwater exploitation and piezometric level evolution 2005–2013 (DGRE 2013)

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basin, Fortuna (Oligocene) reservoir is affected by normal faults post-Oligocene which reveals a homogeneous thickness towards the basin. Miocene reservoir reveals an important thickness varying from the eastern to the western part of this basin; the most important thickness is located to the centre of Sisseb El Alem block. This variation is due to the synsedimentary fault affecting these series. Major faults crossing all of Oligocene and Mio-Plio-Quaternary reservoirs allow the communication between the shallow and the deep groundwater. To the east of this thrust, the Kalaa El Kebira flexural basin is highlighted. The Miocene series have a maximum thickness comparing with those in the Sisseb El Alem basin, which shows a very important subsidence priorMiocene. The thickness of the Oligocene series decreases from east to west in this region. The waterproof in the study area is formed with an important clay series presenting the Cherahil Formation (Upper Eocene). In this seismic section, the main supply sources of Oligo-Miocene deep groundwater are the Draa Essouatir and the Essiouf Elhaouita outcropping structures. The water infiltration is facilitated by major accidents which provide the communication between aquifers. Lithologic and the wire line logging correlation trending NE–SW and NS of petroleum wells (Fig. 4) identify the different Oligocene and Mio-Pliocene reservoir layers towards Sisseb El Alem and Kalaa Kebira blocks. These seismic reflection lines and also their lateral and vertical facies and thickness changes (Fig. 4) are controlled by major faults trending ENE–WSEW to E–W. These sandy levels are separated by impermeable and semi-impermeable levels formed by clay and sandy clay characterized by a clay percentage higher than 50 %. GR and PS curves of Oligocene deposits highlight six lenticular sandy bodies characterized by different facies and thickness presented in the gutter by clay percentage lower than 20 %; this series reveals only three levels to the high zones, and it is absent in the Rouisset (PP8) and Ktifa (PP4) zones. The Miocene reservoirs are absent in the wells to the northern part of the study area (PP9, PP4, PP8, PP2); this lack of deposits is due probably to a non-deposition and/ or important erosion. The Saouaf Formation (Serravalian– Tortonian) is composed of six channelized lenticular reservoir levels changing laterally to four, three and only two levels in PP5 well; these levels are separated by clays which are composed in the southern side of the study area by alternated sands with lignite and sandstones intercalated with clay. To the north-east, deposits contain more clay and sandy clay which shows the deepening of the basin to the eastern side. Beglia Formation constituted by three sandy and channelized lenticular levels presents the

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Fig. 3 EW geoseismic section (L1) showing the OligoNeogene horizon structuring and thickness variation through Sisseb El Alem basin

Fig. 4 NE–SW Wireline logging correlation of Oligocene and Mio-Plio-Quaternary deposits showing sandstones facies and thickness distribution reservoirs levels

same variation than the Saouaf one; it contains more clay to the east. Segui reservoir is presented by the most important thickness and sandy levels (from 7 to 8 levels) to the south of Sisseb El Alem. To the center and the east it shows between seven and four sandy levels with a heterogeneous facies.

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Materials and methods Data collection and analysis A total of 39 water samples were collected from private and public wells in Mai 2014 (Fig. 1). In situ measurements (pH, electrical conductivity (EC), temperature and salinity) were

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done in anaerobic conditions. Water samples were transported to the Laboratory in polyethylene bottle and in an icebox for further analysis. Then, samples were filtered using 0.45 lm Millipore filter paper and stored at 4 °C prior to analysis. The major ions concentrations (Na?, Ca2?, Mg2?, K?) were determined by the spectrometry of atomic absorption type Perkin Elmer associated to graphite furnace. Nitrate was determined by the colorimetric method. The chloride and sulphate titrations are made according to the Mohr and the nephelometric methods, respectively (Rodier 1984). The alkalinity which is attributed primarily to the presence of bicarbonates (HCO3-) was carried out by the volumetric method (Rodier 1984). Total dissolved solids were measured by evaporation and calculation methods (Hem 1991) of pre-filtered sample to dryness.

Methods Evaluation of groundwater quality for drinking purposes The total hardness and the water quality index parameters are chosen based on the data availability and also their relative importance on the defining of the water quality for human use prescribed by the (WHO 2004) for public health purposes. We compared each parameter to the standard limit of the stipulated parameter list for drinking water of (WHO 2004). The total hardness (TH), which is considered as an important parameter for assessing water quality for drinking use, was calculated using the formula (Todd 1980; Hem 1985; Ragunath 1987): TH ðCaCO3 Þ mg=L ¼ 2:497 Ca2þ þ 4:1115Mg2þ

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Step two is the ‘‘relative weight calculation’’: The relative weight (Wi) is calculated with the following equation: wi ð2Þ Wi ¼ Pn i¼1 wi where Wi is the relative weight, wi is the weight of each parameter and n is the number of parameters. The calculated relative weight (Wi) values of each parameter are given in Table 1. Step three is ‘‘quality rating scale calculation’’: The quality rating scale (qi) for each parameter is calculated by dividing its concentration in each water sample by its respective standard (WHO 2004) (Table 1) multiplied by 100. qi ¼

Ci  100 Si

ð3Þ

where qi is the quality rating, Ci is the concentration of each chemical parameter in each water sample in milligrams per liter and Si is the (WHO 2014) standard for each chemical parameter. Then, for estimating WQI, SI is firstly determined for each chemical parameter with the following equation: SIi ¼ Wi  qi X WQI ¼ SIi

ð4Þ ð5Þ

where SIi is the subindex of ith parameter, qi is the rating based on concentration of ith parameter, n is the parameters number. Finally, a map of WQI was produced by computing the individual point data and then plotted using Arc GIS (Ver. 10.2).

ð1Þ

where the concentrations of Ca2? and Mg2? are represented in mg/L. The water quality index (WQI) consists of obtaining one value that summarizes the overall effects of the chemical compound effect of individual water quality characteristic on the global quality of water for human consumption (Tiwari and Mishra 1985; Chung et al. 2014). It has been used by many researchers to assess water resources quality (Jayakumar and Siraz 1997; Shing and Hasnain 1999; Stetzenbach et al. 1999, 2001; Sindhu and Sharma 2007; Santosh and Shrihari 2008; Aly et al. 2014; Chung et al. 2014; Srinivasamoorthy et al. 2014 ). The WQI calculations are used which involve three successive steps (Horton 1965; Subramani et al. 2005; Yidana and Yidana 2010; KetataRokbani et al. 2011; Lateef 2011; Al-hadithi 2012). Step one is the‘‘assigning weight’’: For each parameter a weight (wi) has been assigned according to its relative importance as shown in Table 1.

Evaluation of groundwater quality for irrigation purposes An evaluation of the water quality used for irrigation is primordially since it can have a negative impact on crop growth. Consequently, it is examined by several parameters: –

The Sodium Adsorption Ratio (SAR) values were calculated for each well by the following equation given by Richards (1954) as: Naþ SAR ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi Ca2þ þMg2þ 2

–

ð6Þ

where the concentrations of Na?, Ca2? and Mg2? are represented in meq/L. The sodium percentage (Na %) is calculated using the formula:

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Table 1 Relative weight of chemical parameters (Ramakrishnalah et al. 2009; Lateef 2011)

Results and discussion

Chemical parameters (mg/L)

World Health Organization (WHO 2011)

Weight (wi)

Relative weight P Wi ¼ wi = ni¼1 wi

pH

6.5–8.5

3

0.091

Hardness

500

2

0.061

TDS

600

4

0.121

Calcium

75a

2

0.061

Magnesium

50a

2

0.061

The physico-chemical parameters of the sampled groundwater are shown in Table 2. Groundwater is mildly alkaline with pH ranging from 7.3 to 8.6 with an average value of 8.01. Based on the pH values and the average salinity of the groundwater, this water is prescribed for drinking purposes according to the (WHO 2004). The electric conductivity ranged between 552 and 5560 lS cm-1 and from 0.2 to 2.9 g L-1, respectively.

Potassium

12

2

0.061

Sodium

200

2

0.061

Bicarbonate

120

2

0.061

Chloride

250

3

0.091

Sulfate

250

3

0.091

Nitrate

10

5

0.152

0.5

3 P wi = 33

0.091 P Wi = 0.91

b

B

Total a

WHO (2004)

b

B was not used in this study

Na ð%Þ ¼

ðNaþ þ Kþ Þ  100 ðCa þ Mg2þ þ Naþ þ Kþ Þ 2þ

Assessment of the groundwater quality Groundwater chemistry data which are presented in Table 2 have been utilized as a tool to evaluate their suitability for drinking and irrigation purposes. Groundwater quality for drinking purposes

ð7Þ

–

where the concentrations of Na?, K?, Ca2? and Mg2?are reported in meq/L. The residual sodium carbonate (RSC) index is calculated by the following equation (Ragunath 1987):  2þ  2 RSC ¼ ðHCO þ Mg2þ ð8Þ 3 þ CO3 Þ  Ca

–

where all ions concentrations are expressed in meq/L. The Kelly’s ratio calculated employing the following equation (Kelly 1963): KR ¼

–

ð9Þ

where all the ionic constituents are expressed in meq/L. The magnesium hazard (MH) is calculated using the following equation proposed by (Szabolcs and Darab 1964): MH ¼

–

Naþ ðCa2þ þ Mg2þ Þ

Mg2þ  100 ðCa þ Mg2þ Þ 2þ

ð10Þ

where the concentrations are expressed in meq/L. The permeability index is calculated employing the following equation (Ragunath 1987): pffiffiffiffiffiffiffiffiffiffiffiffiffi ½ðNa2þ þ HCO 3Þ PI ¼  100 ð11Þ 2þ 2þ ðCa þ Mg þ Naþ Þ where all the ions are expressed in meq/L.

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The water used for drinking purposes must meet very high standards like those suggested by World Health Organization (WHO 2004). The total dissolved ions (TDS) is caused primarily by the presence of cations such as calcium and magnesium and anions such as carbonate, bicarbonate, chloride and sulphate in water. The TDS values varies between 726 and 5957 mg L-1 with an average value of 2023.5 mg L-1 for Oligocene aquifer, and between 791 and 4612 mg L-1 with an average value of 2179.63 mg L-1 Mio-Plio-Quaternary aquifer, respectively. All the water samples showed that TH is above the permissible limit of 600 mg/L (Table 1). These higher TDS values may be the influence of anthropogenic sources, such as domestic sewage, septic tanks, and agricultural activities. These high TDS may cause an unfavorable physiological reaction to consumers (Rao et al. 2002). Hardness of the water is the property attributed to the presence of alkaline earths. For Oligocene and Mio-PlioQuaternary aquifers, total hardness varied from 390 to 1875.75 mg L-1 and between 715 and 539.4 mg L-1, respectively. Based on the Sawyer and McCarthy (1967) classification of the TH, groundwater is classified into 0–75 (soft), 75–150 (moderate), 150–300 (high) and 300 (very hard). Thus, all samples fall into the very hard water category. Long-term consumption of extremely hard water might lead to an increased incidence of urolithiasis and cardiovascular disorders (Durvey et al. 1991). The WQI was tested with several selected parameters as pollution indicators (Table 1). The produced map of WQI is presented in Fig. 5. For Oligocene and Mio-Plio-Quaternary, WQI values range from 86.34 to 438.93 and from 109.61 to 386.92, respectively.

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Table 2 Statistics of chemical parameters (all in mg/L, Salinity in g/L and EC in lS/cm) in groundwater samples pH

CE

Salinity

TDS

K?

Na?

Ca2?

Mg2?

SO42-

NO3-

Cl-

PO43-

HCO3-

Oligocene N

20

20

20

20

20

20

20

20

20

17

20

20

20

Mean

8.00

1809.55

0.71

2023.50

4.87

274.62

34.06

174.83

422.39

2.11

73.48

0.12

1082.65

Median

8.01

1522.50

0.55

1821.00

3.96

224.17

28.05

153.94

410.49

1.33

53.25

0.06

965.00

Min

7.50

552.00

0.20

726.00

2.25

116.95

4.00

55.91

119.60

8 9 10-3

14.20

0.01

410.00

Maxi

8.50

5660.00

2.90

5957.00

11.26

955.16

128.25

433.96

735.80

5.99

248.50

0.50

3718.00

SD

0.27

1090.71

0.62

1127.97

2.23

177.81

28.35

84.36

140.29

1.88

55.96

3.13

723.55

Mio-Plio-Quaternary N

19

19

19

19

19

19

19

19

19

19

19

19

19

Mean

7.98

1935.52

0.84

2179.63

5.63

295.06

54.63

191.68

445.75

6.75

83.33

0.08

1199.73

Median Min

8.00 7.30

1678.00 600.00

0.65 0.20

1753.00 791.00

3.62 2.84

243.66 146.19

36.07 4.00

170.91 101.94

387.27 157.16

1.92 0.16

78.10 35.50

0.05 0.01

1061.00 487.00

Max

8.60

3680.00

1.80

4612.00

29.38

653.02

240.48

449.52

990.79

37.50

198.80

0.30

2418.00

SD

0.39

828.66

0.45

1086.76

5.97

132.42

62.53

84.87

211.14

11.37

44.20

0.08

642.22

N number of sampled wells, Min minimum, Max maximum, SD standard deviation

According to WQI classification (Table 3), 10.25 % of the samples fall into the good water, 69.23 % are considered as poor water class, 12.82 % are in the class of very poor water and 7.69 % are unsuitable for drinking. WQI higher values are observed in the north of the study area, and a decrease toward the southern side is observed (Fig. 9). These high WQI values are mainly attributed to the high values of TDS, Mg2?, HCO3-, SO42-, and Na?. Many studies showed high correlation between these parameters and the WQI values (Gupta et al. 2004; Mitra et al. 2007; Deshpande and Ather 2012; WHO 2003; Aly et al. 2014). Groundwater quality for irrigation purposes Several parameters such as pH, EC, sodium percentage, sodium absorption ratio, Kelly ratio, permeability index, residual sodium carbonate and magnesium hazard are used for determining the suitability of groundwater for agricultural uses. Groundwater pH values are between 7.5 and 8.5 with a mean value of 8.0 for Oligocene aquifer and between 7.3 and 8.6 with a mean value of 7.98 for Mio-Plio-Quaternary aquifer. These values are within the safe limit. The water salinity is directly related to the quantity of dissolved salts which is measured by the TDS (total dissolved solids) or the EC (electric conductivity). Plotting the analytical data on the US salinity diagram (USSL 1954; Wilcox 1955) (Fig. 6) shows that majority of water samples indicate high salinity and low sodium water, which can be used for irrigation in almost all types of soil with little danger of exchangeable sodium (Kumar et al. 2007).

Some samples fall into the C4S1 and C4S2 category and are considered unsuitable for irrigation in soils with restricted drainage (Mohan et al. 2000). Excessive sodium in waters may cause undesirable effects in soil properties and alter its permeability. For Oligocene and Mio-Plio-Quaternary, the sodium percentage varies from 13.21 to 62.30 and from14.1 to 45.33 %, respectively. Groundwater classification shows that 2.5 % of samples are considered as good water quality, 64.10 % fall into the permissible category and 33.33 % of samples are in the permissible category (Table 4). Sodium concentration is very important parameter in classifying water use for irrigation as it affects the permeability of soil and induces infiltration problem. According to Richards (1954), water samples having SAR values less than 10 are considered excellent, 10 to 18 as good, 18 to 26 as fair, and above 26 are unsuitable for irrigation use. In the present study, SAR values vary from 2.25 to 7.29 and from 2.19 to 9.53 for Oligocene and MioPlio-Quaternary aquifers, respectively. SAR values indicate that all wells are excellent for irrigation use (Table 4). The Kelly ratio is also used to determine the hazardous effect of sodium on water quality for irrigation purposes. It range between 0.46 and 1.10 and from 0.39 to 0.97 for Oligocene and Mio-Plio-Quaternary aquifers, respectively. The majority of water samples (94.87 %) are suitable for irrigation, and 5.13 % of wells which have a Kelly’s ratio [1 are considered unsuitable for irrigationsince they contaun an excess level of Na? (Table 4). The use of the permeability index (PI) may help in assessing the soil permeability which is affected by longterm use of irrigation water. PI values ranges from 423 to

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Table 3 Water quality classification based on WQI value (Ramakrishnalah et al. 2009; Ketata-Rokbani et al. 2011) Classification of drinking water quality WQI range

Class

Type of water

\50

I

Excellent water

50–100

II

Good water

100–200

III

Poor water

200–300

IV

Very poor water

[300

V

Water unsuitable for drinking

4209.24 and from 306.55 to 1038.39 for Oligocene and Mio-Plio-Quaternary aquifers, respectively. These values fall into the water class III which is categorized as unsuitable for irrigation (Doneen 1964; Raghunath 1987; Table 4). The excess sum of carbonate and bicarbonate in groundwater over the sum of calcium and magnesium also influences the quality of water used for agricultural activities (Raju 2007). The residual sodium carbonate (RSC) values vary from -3.67 to 22.98 meqL-1 and from 4.19 to 7.39 meqL-1 for Oligocene and Mio-Plio-Quaternary aquifers, respectively. From the observed values 82.05 % of the samples are considered safe for irrigation use.

Fig. 5 Spatial distribution map of WQI values for the groundwater samples

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The magnesium hazard proposed for irrigation depends on alkaline earths ions Ca2? and Mg2? which maintain a state of equilibrium in most groundwater (Hem 1985). Excess Mg2? in groundwater during equilibrium will adversely affect the soil quality rendering it alkaline resulting in decrease of crop yield (Kumar et al. 2007). In the analysed groundwater samples, the MH varies from 46.92 to 92.33 and from 60.75 to 93.50 for Oligocene and Mio-Plio-Quaternery aquifers, respectively. All samples have MH values [50 and thereby are considered harmful and unsuitable for irrigation purposes (Table 4). Hydrochemical study Hydrochemical concepts can help to elucidate mechanisms of flow and transport in groundwater systems, and unlock an archive of paleoenvironmental information (Hem 1992; Pierre et al. 2005). The major ions of the Oligocene and Mio-Plio-Quaternary aquifers (Table 2) were plotted on the Piper trilinear diagram (Piper 1944), to distinguish the different waters types in the studied aquifer system. Three major hydrochemical facies were obtained (Fig. 7): HCO3/Mg, HCO3/ Na and SO4/Mg water types.

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Fig. 6 Wilcox diagram of irrigation water quality

Spatial distribution of major ions and statistical analysis The spatial variation of groundwater dominant dissolve ions highlights the relative importance of the water chemistry, complex weathering process, ion exchange and agricultural influence. A spatial variation map is realized (Fig. 8). The order of abundance of chemical concentration of the cations is Na? [ Mg2? [ Ca2? [ K?. The concentrations of Na? and K? from 116.95 to 955.16 mg L-1 and vary from 2.25 to 29.38 mg L-1, respectively. Among 39 samples, 71 and 2 % of the samples, respectively showed higher Na? and K values than their corresponding WHO (2011) standard of 200 and 10 mg/L. The existence of the plagioclase feldspars (albite), K-feldspar (orthoclase) could be the possible source of Na? and K?, respectively, in the groundwater in the study area. Clay mineral (illite) that has a great percentage could be the main resource of K?. We note that the excess of Na? over K? is perhaps because K-feldspar in the area is more resistant to weathering than albite and also to the overexploitation of groundwater. Among the alkaline earths, the concentration of Ca2? and Mg2? are in the range of 4.00 to 240.48 mg L-1 and of 55.91 to 449.52 mg L-1, respectively. Only 2 % of the samples were having Calcium values above the permissible limit of 75 mg L-1. While, all samples exceed the permissible limits of 50 mg L-1 for magnesium.

The leaching of anhydrite, gypsum, dolomite and calcite are probably the source of calcium in the groundwater. The presence of dolomite in the sedimentary rocks of the study area might be the source of the Mg2?. The higher magnesium values may be due to the application of sewage. Bicarbonate is the most abundant anion in all locations and varies from 410 to 3718 mg L-1. All groundwater samples exceeded the standard limit of bicarbonates (120 mg L-1). The reaction of carbonate minerals with carbon dioxide gas (CO2) and the dissolution of CO2 from the possible mechanisms may supply bicarbonate into groundwater. To the north of the sector (Saouaf, Sisseb) regions, geological outcrops are represented by limestones and sandstones of the Upper Cretaceous and Eocene which might explain the higher concentration of the HCO3- in the Oligocene and Mio-Plio-Quaternary groundwater (Fig. 3). Sulphate is the second most common anion with concentrations range from 119.6 to 990.79 mg L-1. To the south of the sector, in the Sbikha region, aquifers are richer in clay and sulfate minerals such as anhydrite and gypsum are probably the main sources of sulfate in the groundwater. The majority of samples exceeded standard limit of sulphate which 250 mg L-1. These higher concentrations may be due to the dissolution of filtering water, leaching from fertilizers and municipal waste (Singh 1994) and desulphidation reaction in anaerobic environment, since groundwater is found to be poor in nitrate. Excess concentrations of sulfate might cause laxative effect on the

123

123

PI

KR

2,5,6,8,9,11,12,13,15,16,19,24,25,26,29,31,32,34,35

Moderate Unsafe

25–75

[75

9,35

Unsuitable Safe

Unsuitable Suitable

[80

\1

[1

Doubtful

60–80

\25

1,2,3,4,5,6,7,8,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,36,37,38,39

Permessible

40–60

1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39

33,34,35,36,38

1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,37,39

0

0

0

0

0

Excellent Good

20–40

9,25,31,35

12,34,37

1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39 1,2,3,4,5,6,7,8,10,11,13,14,15,16,17,18,19,20,21,22,23,24,26,27,28,29,30,31,33,36,38,39

0

0

0

1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39

0

0

0

\20

Marginally suitable Not suitable

1,25–2,5

[2,5

Hard Very hard Safe

150–300

[300 \1,25

Soft Moderately hard

75–150

Unsuitable

[50

\75

Unsuitable Suitable

[80

\50

Doubtful

60–80

1,3,4,7,10,14,17,18,20,21,22,23,27,28,30,33,36,37,38,39

0

6,12,14,17,31,32,38

1,2,3,4,5,8,10,11,15,16,20,21,22,23,24,25,26,27,28,33,34,35,36,37,39

13,18,29

0

Number of wells

Page 10 of 17

SAR

RSC

TH

MH

Permessible

40–60

Unsuitable

[3000 Excellent

Doubtful

2000–3000

Good

Permessible

750–2000

20–40

Good

250–750

\20

Excellent

\250

EC

Na%

Class

Range

Paremeters

Table 4 Classification of groundwater quality based on suitability of water for irrigation purposes

746 Environ Earth Sci (2016) 75:746

Environ Earth Sci (2016) 75:746

Fig. 7 Piper diagram of the groundwater samples

human system (Hull 1984; Kumar et al. 2007; Arumugam and Elangovan 2009). Chloride concentrations vary from 14.2 to 248.5 mg L-1 which are below the desirable limits of WHO guideline (250 mg L-1). The principal sources of chloride are animal organic matter, sewage from drainages

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and refuse. Also, the huge use of fertilizer in agriculture also plays a vital role as the source of chloride. Nitrate concentrations vary from 0.008 to 37.39 mg L-1. These concentrations are very low and are below the WHO guidelines (10 mg L-1) except for the well n°25 (37.39 mg L-1). Also, phosphorous ions have very low concentrations in the groundwater samples and do not exceed 0.3 mg L-1 (Table 2). This could indicate that there is little or no pollution of the resource or the geology of the area which does not contain the anion. In some areas, the contamination of shallow groundwater due to the excessive application of fertilizers and sewage (Laajili 2014) and thereby these ions could be leached to deeper groundwater. Inter-elemental correlation was made (Table 5) to understand the relationship between different ionic species. The correlation matrix requires normal distribution of all variables (Lawrence and Upchurch 1982; Joliffe 1986; Wold et al. 1987). The pH does not show any strong correlation with TDS or the major ions investigated, which reflect that pH does not play an important role in controlling the groundwater chemistry. The EC, salinity and TDS are highly positive correlated with K? (r = 0.64, 0.63 and 0.68), Na? (r = 0.9, 0.9 and 0.9), Mg2? (0.92, 0.92 and 0.93), SO42- (0.59, 0.57 and 0.68), Cl- (r = 0.87, 0.81 and 0.80) and HCO3- (r = 0.97, 0.97 and 0.96), indicating that

Fig. 8 Spatial distribution of major elements contributing to the groundwater mineralization

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Page 12 of 17

Environ Earth Sci (2016) 75:746

Fig. 9 The mineral saturation indices (SI) of studied water samples

the groundwater is mainly controlled by K?, Na?, Mg2?, SO42-, Cl-, and HCO3- ions which depend on the mineral dissolution and solubility, ion exchange, evaporation, anthropogenic activities, following the topographical features and water flow-path conditions. The Na? shows significant positive correlation with Cl(r = 0.79) and SO42- (r = 0.51), and the Cl- has positive correlation with SO42- (r = 0.47), which indicate the influences of evaporation, agricultural activities on the groundwater system. Sodium also exhibits good positive correlation with magnesium (r = 0.78) which reveals that that they are not involved in the same geochemical processes (Hounslow 1995). There is no relation between Ca2?and HCO3 (r = 0.30) which shows that calcite is not the main source of Ca2? and that bicarbonate high concentration in groundwater is derived from carbonate weathering as well as dissolution of carbonic acid in the aquifers. The most important positive correlations of bicarbonate and sodium (r = 0.93), bicarbonate and magnesium (r = 0.92) that are attributed to the dissolution of carbonates rocks (dolomite) which are present in the sedimentary rocks (Yaich 1997; SETEGUETUNISIE 2004). Rock–water interaction The rock–water interactions control the most transformations on the earth’s surface. The minerals that constitute the rocks react with aqueous solutions; primary minerals are dissolved, and thereby freeing ionic species in solution while secondary minerals precipitate at thermodynamic equilibrium or in oversaturated environment. The alteration processes are usually very complex, so geochemical models have been developed in order to understand and simulate the reaction occurring between a set of minerals, constituting a rock and an aqueous

123

solution at thermodynamic disequilibrium (Clement et al.1994). The Saturation indexes (SI) were calculated using PHREECQ version 3 in order to evaluate the potential chemical reactions of groundwater with respect to mineral phases (Fig. 9). In the present study, groundwater is undersaturated with respect to evaporate and sulphate minerals (halite, gypsum and anhydrite), which indicates that the dissolution of the above mentioned minerals are additional dominant mineralization processes. On the other hand, groundwater samples are found to be oversaturated with respect to carbonate (dolomite, calcite and aragonite). The calcite precipitation, induce the bicarbonate concentration decrease in groundwater, which causes the undersaturation with respect to dolomite and improve the incongruent dissolution of this mineral known as dedolomitization (Cardenal et al. 1994). Ca/Mg ratio decreases and sulfate concentration increases according to the following reaction. CaMgðCO3 Þ2 ðsÞ þ CaSO4 2H2 OðsÞ þ H þ  ! CaCO3 ðsÞ þ Ca2þ Mg2þ þ SO2 4 þ HCO3 þ 2H2 O On the other hand, the SO42- versus Ca2? plot (Fig. 10) shows a more pronounced loss of Ca2? with respect to SO42-. This may be the result of calcite precipitation controlled by gypsum dissolution. The evaporation rate and the water–rock interaction generally govern the water chemistry (Gupta et al. 2008; Subramani et al. 2005). The Gibbs diagram is widely used to assess the distinction between waters controlled by water–rock interaction (i.e., leaching and dissolution), evaporation and precipitation processes (Gibbs 1970; Feth and Gibbs 1971; Uliana and Sharp 2001; Mamatha and Sudhakar 2010; Xing et al. 2013). The Gibbs ratio I for anions and the Gibbs ratio II for cations were calculated using the follow equations:

Environ Earth Sci (2016) 75:746

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Table 5 Correlation matrix of the geochemical variables results (marked correlations are significant at p \ 0.05) pH

K?

pH

1.00

K?

-0.29

1.00

Na?

-0.32

0.40

2?

Na?

Ca2?

Mg2?

So24

NO3-

Cl-

PO43-

EC

Salinity

TDS

1.00

Ca

-0.37

0.06

0.25

1.00

Mg2?

-0.33

0.80

0.76

0.17

1.00

So24

-0.35

0.71

0.51

0.27

0.67

NO3-

-0.40

0.51

0.16

0.58

0.43

0.36

1.00

Cl-

-0.26

0.49

0.79

0.24

0.74

0.47

0.22

1.00

0.07

0.09

0.05

-0.31

0.08

0.04

-0.15

0.21

1.00

PO43-

HCO3-

1.00

HCO3-

-0.34

0.61

0.92

0.30

0.92

0.53

0.37

0.78

-0.01

1.00

EC Salinity

-0.41 -0.43

0.64 0.63

0.90 0.90

0.31 0.33

0.92 0.92

0.59 0.57

0.36 0.38

0.87 0.81

0.03 -0.03

0.97 0.97

1.00 0.98

1.00

TDS

-0.44

0.68

0.90

0.33

0.93

0.68

0.38

0.80

0.06

0.96

0.96

0.96

1.00

Bold values indicates reflected the good correlation

  Gibbs ratio I ðfor anionÞ ¼ Cl = Cl þ HCO 3   Gibbs ratio II ðfor cationÞ ¼ Naþ þ = Naþ þ Ca2þ From the graphical plots (Fig. 11), it is observed that the majority of the water samples are falling in rock dominance area, while few samples are under evaporation dominance, indicating that the source of mineral constituents in water is mainly from the dissolution of rock through which water is circulating. The two chloroalkaline indices CaI1 and CaI2 (Schoeller 1965, 1967) using the formulae: CAI1 ¼ fCl  ðNaþ þ Kþg=Cl ð12Þ      CAI2¼ fCl  ðNaþ þK þ Þg= SO2 4 þHCO3 þCO3 þNO3 ð13Þ where, the concentration is in meq/L. When there is an exchange between calcium and magnesium in the groundwater with sodium and potassium in the aquifer material, both above indices will be negative,

Fig. 10 (Ca2?) versus (SO42-) diagram

and if there is a reverse ion exchange, then both indices will be positive (Schoeller 1965, 1967). In this study case, CAI1 values (Fig. 12) ranged from -8.59 to -0.24 and from -11.82 to -0.48, respectively for Mio-Plio-Quaternary and Oligocene aquifer, and CAI2 values (Fig. 12) varied from -0.20 to -0.04 and from -0.21 to -0.06 for Mio-Plio-Quaternary and Oligocene aquifer, respectively. This observation indicated that the normal ion exchange is the dominant process in the groundwater. Thus, the aquifer materiel is important sources of water dissolved solids (Singh and Hasnain 1999; Adrian et al. 2007). The minerals weathering and dissolution can be suggested by the plot of (Ca2? ? Mg2?) and (SO42- ? HCO3-) that could provide information on the relative importance of the main minerals contributing to groundwater mineralization (Datta and Tyagi 1996). All samples fall above the equilibrium line due to the excess of SO42- ? HCO3- indicating that these ions have resulted from weathering of carbonates and sulphate mineral ions (Datta and Tyagi 1996; Rajmohan and Elango 2004) and that ion exchange ion process is the most dominant. Therefore, the excess of charge of SO42- ? HCO3- must be balanced by alkalisions (Na? ? K?). Also relative excess of SO42-with respect to Ca2? (Fig. 10) suggests that there is another supplementary mineralization process, probably related to the modification by reverse cation exchange phenomenon. During this process, Ca2? in the solution is exchanged with Na2? previously absorbed on the surface of clay minerals in the aquifer matrix (Fig. 13). Therefore, the main hydrogeochemical processes that typically control the groundwater mineralization are dissolution of evaporates (halite, gypsum and anhydrite), dedolomitization and cation exchange processes.

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Page 14 of 17

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Fig. 11 Gibbs diagram

Fig. 12 Chloro-alkaline indices 1 and 2 (CAI 1and CAI 2) for groundwater in the study area

Conclusion The Sisseb El Alem aquifer is investigated to evaluate the water quality for drinking and irrigation purposes and identification of hydrogeochemical mechanisms. Assessment of water quality in the study area based on WHO standard guideline revealed that the wells used for drinking are classified as very hard water as the TH and TDS are far beyond the permissible limits. The WQI showed that more than two-thirds of the water samples fall into the poor water class. The high WQI obtained values were attributed to the high values of pH, TDS, Mg2?, HCO3-, SO42-, and Na?. Also, the WQI values showed that the Oligocene aquifer samples are classified as good water for human consumption and they correspond to the wells designated for drinking purposes. However, the quality of Oligo-MioPlio-Quaternary groundwater was found to be suitable for irrigation purposes based on different parameters like (EC, SAR, Na %, KR, salinity diagram). Although, based on the RSC, MH, and PI, the groundwater quality needs to be

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Fig. 13 (Ca2?? Mg2?) versus (SO42- ? HCO3-)

controlled and measures are necessary to ensure sustainable safe use for the resource. Water quality in the study area is slowly reaching alarming stage and proper planning is essential in this venture to preserve the fragile ecosystem. The results of hydrochemical analysis of groundwater revealed three major facies: HCO3/Mg, HCO3/Na, and

Environ Earth Sci (2016) 75:746

SO4/Mg water types which are mainly due to the geology of the study area. The distribution of major anions and cations and occurrence of different hydrochemical facies suggest that the composition of groundwater is influenced by water–rock interaction. Further, the correlation of different major elements with the TDS values showed that groundwater mineralization is mainly dominated by K?, Na?, Mg2?, SO42-, Cl-, and HCO3- ions. The aquifer material is the primary source of dissolved in the water. Ca2? or Mg2? in groundwater was exchanged with Na? and K? in the aquifer material except for the well n°39 which has positive chloro-alkaline indices which indicates a base exchange of Na? and K? ions in water that are exchanged with Mg2? or Ca2? ions in weathered materials. The saturation index suggest that all water samples indicate oversaturation with respect to calcite (CaCO3), aragonite (CaCO3) and dolomite CaMg (CO3)2 and possess a precipitation tendency, while evaporate minerals (anhydrite, gypsum, and halite) were unsaturated and thus would dissolve during groundwater flow. The Gibbs plot showed that the groundwater was influenced by the weathering of the geologic material and evaporation dominance. According to the Oligo-Miocene mineral composition and the geochemical results of groundwaters, these are important intercommunications between these aquifers. Acknowledgments This work is a part of the results of the research Project—2002–2014—of ‘‘Deep Aquifers in Eastern Tunisia Sahel regions’’ of the Georesource Laboratory in the Centre of Water Researches and Technology of the Borj Ce´dia Technopark in collaboration with the ‘‘Direction Ge´ne´rale des Ressources en Eaux’’ of the Agriculture Ministry and financed by the Ministry of Higher education and scientific research of Tunisia. We would like to express our gratitude and thanks to the technicians and engineers staff of Kairouan and Sidi Bouzid water resources regional departments, and also to the researchers and staff members of Georesource and waste water treatment laboratories, for their help and assistance, during the field survey and laboratory analysis.

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