# Characterization of Recharge Mechanisms and Sources of Groundwater Salinization in Ras Jbel Coastal Aquifer (Northeast Tunisia) Using Hydrogeochemical Tools, Environmental Isotopes, GIS, and Statistics

Authors: Jamila Hammami Abidi; Boutheina Farhat; Abdallah Ben Mammou; Naceur Oueslati
Journal: Journal of Chemistry
 (2017)

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## Abstract

Groundwater is among the most available water resources in Tunisia; it is a vital natural resource in arid and semiarid regions. Located in north-eastern Tunisia, the Metline-Ras Jbel-Raf Raf aquifer is a mio-plio-quaternary shallow coastal aquifer, where groundwater is the most important source of water supply. The major ion hydrochemistry and environmental isotope composition (δ18O, δ2H) were investigated to identify the recharge sources and processes that affect the groundwater salinization. The combination of hydrogeochemical, isotopic, statistical, and GIS approaches demonstrates that the salinity and the groundwater composition are largely controlled by the water-rock interaction particularly the dissolution of evaporate minerals and the ion exchange process, the return flow of the irrigation water, agricultural fertilizers, and finally saltwater intrusion which started before 1980 and which is partially mitigated by the artificial recharge since 1993. As for the stable isotope signatures, results showed that groundwater samples lay on and around the local meteoric water line LMWL; hence, this arrangement signifies that the recharge of the Ras Jbel aquifer is ensured by recent recharge from Mediterranean air masses.


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## Body

## 1. Introduction

The hydrogeology of coastal aquifers has been studied intensively during the past decades, stimulated by both scientific interest and societal relevance [1]. Coastal areas throughout the Mediterranean face salinization problems of groundwater which is the major source of water supply especially for drinking and agricultural sector. The imbalance between abstraction and natural recharge rates causes an overexploitation of groundwater resources resulting in declining groundwater table, water quality degradation, and crop damage.A number of aquifers in coastal zones are being increasingly exploited and affected ([2–6]). For instance, groundwater contamination and decline of water levels have been reported in Tunisia [7–13] and in many countries around the world. It has been reported in India [14], Jordan [15], Australia [16], USA [17], China ([18, 19]), Netherland [1], and among many others.In semiarid coastal regions of north-eastern Tunisia, such as Ras Jbel plain, the groundwater is usually the main resource used for irrigation and drinking purposes. Nevertheless, salinization is becoming a common problem affecting groundwater resources. Groundwater exploitation of the Ras Jbel aquifer began in 1949 and has increased each year since 1980. Under pressures of population, climate change, and pollution, the aquifer faces substantial challenges in the management of scarce freshwater resources. During the last four decades, the shallow aquifer groundwater has been overexploited through excessive, uncontrolled pumping mainly for domestic and agricultural purposes [20]. Salinization due to seawater intrusion and decreasing groundwater levels has recently been identified [21]. Unplanned and substantial withdrawals of groundwater from the shallow aquifer of Ras Jbel have resulted in severe water level decline of up to 7 m in some areas and high total dissolved solids (TDS) contents reaching 8000 mg/l. Reports of increasing salinity of groundwater supplies in the area suggest a need to define the sources of salt water. It is also useful to study the recharge mechanisms as well as the mixing fresh water/saline water.Stable isotope and geochemical techniques have been used in groundwater studies of coastal aquifers worldwide [22–25] for determining the origins of groundwater salinization in aquifers and processes that affect water chemistry, such as rock weathering, evaporation, atmospheric precipitation, and cation exchange. Consequently, studying stable isotope and geochemical techniques can significantly improve our understanding of groundwater hydrodynamical processes and chemical evolution [26]. In the present study, environmental isotopes (δ18O, δ2H) in conjunction with hydrochemistry (major ions) were employed (1) to define the potential sources and different mechanisms of groundwater salinization in the study area (2) to discuss the chemical evolution of groundwater and (3) to explain groundwater recharge and discharge in the coastal plain of Metline- Ras Jbel- Raf Raf.


## 2. Study Area

The Metline-Ras Jbel-Raf Raf plain, which covers a total area of about 50 km2, represents one of the most important agricultural regions in north-eastern Tunisia (Figure 1). It is characterized by a semiarid, “Mediterranean” climate with mild, wet winters and warm, dry summers [27, 28]. The average annual precipitation ranges from approximately 258 to 993 mm (Figure 2). Geologically, it is limited to the south by Jbel Djaouf, En Nadhour, and Ed Demina, to the southwest by Jbel Sidi Saleh, Hakima, and El Faouar, to northwest by Jbel Bab Banzart, Sidi Bou Choucha, and Touchela, to the north and northeast by the Mediterranean sea. The plain of Metline-Ras Jbel-Raf Raf is a wide basin of collapse, formed by a subsidence followed by an alluvial and recent sedimentation. It is affected by folding and faults in NW-SE and SSW-NNE directions. Sedimentary series extend from Miocene to Quaternary. The lithological description of these sediments [28–30] reveals that the Miocene is represented by the Kechabta and Wadi Bel Khedim formations. The Kechabta formation has a thickness of about 1000 m and consists of alternation of marls and fine sandstone benches. The Wadi Bel Khedim formation is of 250 m thickness. At the east of Raf Raf, it is composed of large outcrops of gray marls with gypsum benches. The Quaternary series unconformably overlie the Miocene series and is divided into seven units (from bottom to the top qm1, Aa, qm2, Qpa, Qp-t, D and a).Figure 1
Geological and location map of the study area [28–30].Figure 2
Yearly precipitation in Metline-Ras Jbel-Raf Raf plain [64, 65].Hydrologically, the Quaternary series and the current formations, characterized by their extension and their good permeability, host the shallow aquifer of Ras Jbel. This aquifer is recharged by local infiltration on the plain, by water flowing from the surrounding hills, and from the different rivers crossing the plain: Wadi Beni Ata and Wadi Ali in Beni Ata region, Wadi El Kantra, El Blaat, and El Ma in Ras Jbel region, Wadi Sandid draining the zone of Raf Raf and Wadi El Kantra in the region of Dar El Khaddar. Pumping tests showed that transmissivity can reach 15.10−4 m2/s. The most transmissive areas are the low alluvial plain of Bahirat Beni Ata, the low alluvial area of Wadi El Krib and El Aouinet, and the upstream area of Ain Cherchar, Ain Ezzaouia, Ain Kassa, and Ain El Hammam, as well as the sandstone dune of Ain El Mestir and Ain Mahloul.The shallow aquifer of Ras Jbel is affected by natural and anthropogenic factors like evaporation, irrigation, pumping, and so forth. The aquifer is tapped by several private and state owned wells. In the period between 1985 and 1990, the exploitation rate was estimated at 13,5 Mm3/year, which exceeded the renewable resources evaluated at 8,44 Mm3/year [31]. The total number of dug wells has been estimated to be 1387 in 1985, 1396 in 1990, and 1563 in 2005. In 2005, the exploitation rate was estimated at 10,27 Mm3/year (Figure 3). The massive exploitation of aquifer resources in response to the heavy pumping caused a drop in the water level (Figure 4) and the deterioration of water quality. In 1949, the salinity of the groundwater varied between 648 and 1692 mg/l [32]. The investigations carried out by the DGRE between 1985 and 1993 through several monitoring wells revealed the existence of a very saline groundwater. The degradation of the water quality has been detected mainly in coastal areas where salt concentrations exceeded 15 g/l in 1985 and 8 g/l in 1993 and in the depression of Bahirat Beni Ata where the ante-quaternary substratum is below the sea level [21].Figure 3
Evolution of the exploitation rate and the monitoring well number of the shallow aquifer of Ras Jbel during 1966 and 2005 [30, 31].Figure 4
Piezometric contour maps of the study area [31].


## 3. Methods

### 3.1. Water Sampling and Chemical Analysis

Ninety-four samples (including pumping wells and piezometers) were collected for geochemical analysis (major elements) and isotopes (δ2H, δ18O) during the wet and the dry season of March and July 2007 (Figure 5). Sampling locations were recorded using a potable GPS device. Prior to sampling, all wells were pumped for several minutes to eliminate the influence from stagnant water. Samples were collected in cleaned polyethylene bottles, tightly capped and stored at 4°C until analysis. Electrical conductivity (EC), salinity, and pH were measured in the field using a portable conductivity, salinity, and pH meter.Figure 5
Location of sampled wells and piezometers in the study area.Chemical analyses were done using a Varian 730-ES ICP Optical Emission Spectrometer for cations and using ion chromatography (DX-120, Dionex, USA) for anions.HCO3- was measured by titration (Hach, USA). Samples for stable isotope analysis were collected according to the procedures described by Clark and Fritz [33]. Isotopic analyses were conducted in the isotopic laboratory of the department of Hydrology and Geo-environmental Sciences of the Faculty of Earth and Live Sciences of the Free University of Amsterdam. Isotopic ratios are expressed in per mil (δ) and oxygen and hydrogen isotope analyses were reported to d notation relative to Vienna Standard Mean Oceanic Water (V-SMOW), where d=[(Rs/RVSMOW)-1]×1000, Rs represents either the 18O/16O or the 2H/1H ratio of the sample, and RSMOW is 18O/16O or the 2H/1H ratio of the SMOW. Typical precisions are ±0.1 and ±1% for oxygen-18 and deuterium, respectively.


### 3.2. Statistical Analysis

The physicochemical parameters and chemical composition of the groundwater samples are presented in Table1. All the acquired data were integrated into hydrogeochemical database in order to study the groundwater quality and to identify the groundwater salinization processes that contributed to the acquisition of the actual chemical composition.Table 1
Chemical data of sampled wells and piezometers in the Ras Jbel aquifer.
Well
EC
pH
TDS
Ca2+
Mg2+
Na+
K+
Cl−
S
O
4
2
-
H
C
O
3
-
EC
pH
TDS
Ca2+
Mg2+
Na+
K+
Cl−
S
O
4
2
-
H
C
O
3
-
Wet season
Dry season
1
3670
7,41
2369
225
89
443
10
999
298
305
5430
7,2
3630
299
140
757
12
1792
343
287
2
3990
7,05
2519
447
57
413
4
1022
307
270
3760
7,21
2446
447
58
376
1
989
326
250
3
3840
6,8
2649
442
54
425
11
997
384
338
3480
7,05
2451
421
48
392
9
918
356
308
4
4120
7,1
3166
368
72
647
5
1021
742
311
3900
7,2
2612
327
63
506
2
789
626
299
5
6300
6,9
4110
520
89
738
7
1390
1005
361
5530
7,06
4323
501
94
731
4
1599
1040
354
6
5080
6,95
3345
403
81
666
8
1160
661
366
3850
7,15
2832
363
66
499
5
953
598
348
7
5790
6,9
3630
560
115
550
4
1457
635
309
4740
7
3231
523
103
471
3
1181
633
317
8
3730
6,9
2306
286
115
284
20
895
377
329
3560
7,11
2407
353
135
294
12
876
421
317
9
5660
7,03
3800
368
129
881
11
1487
563
361
4660
7,16
3126
339
96
609
7
1248
498
329
10
3530
7,3
2384
249
59
388
25
788
589
287
2840
7,63
1989
258
46
347
20
610
489
220
11
4480
7,12
3260
379
72
646
18
989
820
337
3650
7,19
2674
334
59
500
13
774
683
311
12
3250
7
2142
230
55
346
37
705
477
293
3160
7,35
2360
285
55
434
37
720
543
287
13
2770
7
1658
216
45
264
31
474
352
277
2540
7,35
1710
243
41
262
29
487
380
268
14
2480
7,65
1972
278
46
337
24
659
382
246
2860
7,49
2040
263
50
343
23
662
462
238
15
6250
7,96
4089
466
86
857
96
1463
811
310
4230
7,35
3049
353
71
605
26
866
684
445
16
4190
7,6
2480
258
78
444
22
830
619
231
3520
7,38
2392
276
70
421
19
766
598
244
17
3990
7,5
2715
274
49
550
107
775
460
500
3290
7,7
2497
280
50
426
80
652
413
598
18
2920
7,2
2046
221
56
330
79
472
444
445
2240
7,29
1841
199
45
289
75
444
363
427
19
2730
7,75
1817
236
54
285
25
451
382
381
2250
7,3
1680
215
46
256
31
427
395
311
20
4020
7,23
2747
208
131
525
6
1011
481
386
3360
7,33
2389
206
124
410
3
872
384
390
21
1240
7,78
819
48
36
165
7
289
102
173
2120
7,55
1317
104
57
270
5
639
108
134
22
3280
7,05
2358
258
55
377
35
844
515
275
2910
7,65
1835
230
42
338
32
589
366
238
23
1573
7,68
924
84
19
200
6
276
89
250
1131
7,82
783
73
12
182
3
217
88
207
24
5170
7,15
2891
505
75
510
8
1185
407
201
4060
7,05
2697
490
67
433
5
1066
436
201
25
4610
7,3
2910
189
113
576
7
916
652
458
3880
7,33
2889
211
123
590
4
878
650
433
26
5050
7,3
2330
7,33
1666
216
55
270
12
464
264
387
27
3400
7,55
1938
255
65
287
27
594
415
296
2720
7,33
1928
257
62
312
35
568
371
323
28
3160
7,6
1662
178
48
289
87
478
356
226
2520
7,39
1910
279
57
280
16
593
393
293
29
2950
7,89
2176
187
66
419
6
713
587
198
30
3580
7,2
2353
199
80
437
11
819
613
195
3240
7,5
2217
205
72
427
11
732
582
189
31
3090
7,5
2187
225
71
394
10
710
560
217
3240
7,54
2330
228
68
424
7
766
637
201
32
3490
7,6
2317
231
69
479
10
749
560
221
3830
7,35
2804
269
80
572
7
866
723
287
33
4290
7,1
2886
358
70
404
20
954
729
351
5080
7,75
3608
454
90
654
23
1107
884
397
34
3640
7,25
2648
292
66
520
15
851
591
315
3410
7,35
2429
305
67
401
12
764
575
305
35
3860
7,25
2836
326
81
550
27
874
634
344
3420
7,51
2487
304
71
455
14
756
571
317
36
4820
7,95
3253
398
81
472
36
1084
789
393
4110
7,43
3015
348
74
539
38
922
729
366
37
3740
7,45
2390
230
78
412
17
829
607
218
3320
7,32
2441
265
70
474
16
757
609
250
38
2720
7,7
1881
197
55
332
9
591
465
232
3650
7,5
2628
292
71
491
6
821
654
293
39
2080
7,7
1378
169
32
251
11
470
336
110
1817
7,49
1269
158
30
213
8
391
319
153
40
3540
7,4
2454
231
75
419
8
823
620
278
3770
7,19
2727
273
81
489
7
865
696
317
41
5030
7,1
3010
402
81
456
14
1166
689
201
3130
7,67
2233
232
68
431
7
734
578
183
42
2820
7,93
2061
179
65
371
6
683
580
177
44
2980
7,12
1817
236
43
324
78
531
337
270
2090
7,52
1694
198
42
234
64
502
355
299
45
2670
7,1
1694
215
43
277
69
493
316
281
2130
7,4
1553
203
40
258
67
437
294
256
46
2840
7,4
1741
200
55
267
9
555
375
281
3050
7,3
2277
285
69
390
3
770
516
244
47
3310
7,05
1749
300
59
217
3
680
233
256
3170
7,3
2257
389
57
249
2
807
522
232
48
4990
7,06
2856
555
82
400
5
1210
355
250
4120
7,1
2601
560
73
327
2
1084
372
183
EC (μs/cm); TDS, Ca2+, Mg2+, Na+, K+, Cl−, SO42-, HCO3- (mg/l).Piper plots [34],considered as the common method for a multiple analyses on the same graph, are used to represent the different water samples and to distinguish graphically between different water types defined by the Stuyfzand classification (1993). Sample points with similar hydrochemistry tend to cluster together in the diagram [35].Principal component analysis method (PCA) and correlations are a popular method to assess groundwater quality. One of the principle advantages of multivariate techniques such as principal component analysis (PCA) is that they are able to rapidly reveal relationships between a large number of variables. In this study, PCA and correlations are used to identify the possible sources of major ions in groundwater, hydrogeological reactions that may occur in the study area, and dominant factors that control groundwater quality.Gibbs diagrams which are a simple plot of the TDS versus the weight ratio of Na+/(Na+ + Ca2+) or Cl-/(Cl-+HCO3-) are widely used to establish the relationships between the water composition and the lithological characteristics of the aquifer [36]. Three distinct fields, including precipitation dominance, evaporation dominance, and rock weathering dominance, constitute the segments in the Gibbs diagram.Hydrogeochemical Modeling. The equilibrium state of the water with respect to a mineral phase can be determined by calculating saturation index (SI) using analytical data. In this study, saturation indices (SI) were calculated in terms of the following equation [37]: (1)SI=log⁡IAPksT,where IAP is the relevant ion activity product, which can be calculated by multiplying the ion activity coefficientγi and the composition concentration mi, and ksT is the equilibrium constant of the reaction considered at the sample temperature [35]. The geochemical modeling program PHREEQC has been used to evaluate the water chemistry. SI>0 indicates oversaturation and minerals may be subject to precipitation, SI<0 means undersaturation and minerals will dissolve, and SI=0 suggests saturation and minerals are in equilibrium status with respect to the solution [38].


## 3.1. Water Sampling and Chemical Analysis

Ninety-four samples (including pumping wells and piezometers) were collected for geochemical analysis (major elements) and isotopes (δ2H, δ18O) during the wet and the dry season of March and July 2007 (Figure 5). Sampling locations were recorded using a potable GPS device. Prior to sampling, all wells were pumped for several minutes to eliminate the influence from stagnant water. Samples were collected in cleaned polyethylene bottles, tightly capped and stored at 4°C until analysis. Electrical conductivity (EC), salinity, and pH were measured in the field using a portable conductivity, salinity, and pH meter.Figure 5
Location of sampled wells and piezometers in the study area.Chemical analyses were done using a Varian 730-ES ICP Optical Emission Spectrometer for cations and using ion chromatography (DX-120, Dionex, USA) for anions.HCO3- was measured by titration (Hach, USA). Samples for stable isotope analysis were collected according to the procedures described by Clark and Fritz [33]. Isotopic analyses were conducted in the isotopic laboratory of the department of Hydrology and Geo-environmental Sciences of the Faculty of Earth and Live Sciences of the Free University of Amsterdam. Isotopic ratios are expressed in per mil (δ) and oxygen and hydrogen isotope analyses were reported to d notation relative to Vienna Standard Mean Oceanic Water (V-SMOW), where d=[(Rs/RVSMOW)-1]×1000, Rs represents either the 18O/16O or the 2H/1H ratio of the sample, and RSMOW is 18O/16O or the 2H/1H ratio of the SMOW. Typical precisions are ±0.1 and ±1% for oxygen-18 and deuterium, respectively.


## 3.2. Statistical Analysis

The physicochemical parameters and chemical composition of the groundwater samples are presented in Table1. All the acquired data were integrated into hydrogeochemical database in order to study the groundwater quality and to identify the groundwater salinization processes that contributed to the acquisition of the actual chemical composition.Table 1
Chemical data of sampled wells and piezometers in the Ras Jbel aquifer.
Well
EC
pH
TDS
Ca2+
Mg2+
Na+
K+
Cl−
S
O
4
2
-
H
C
O
3
-
EC
pH
TDS
Ca2+
Mg2+
Na+
K+
Cl−
S
O
4
2
-
H
C
O
3
-
Wet season
Dry season
1
3670
7,41
2369
225
89
443
10
999
298
305
5430
7,2
3630
299
140
757
12
1792
343
287
2
3990
7,05
2519
447
57
413
4
1022
307
270
3760
7,21
2446
447
58
376
1
989
326
250
3
3840
6,8
2649
442
54
425
11
997
384
338
3480
7,05
2451
421
48
392
9
918
356
308
4
4120
7,1
3166
368
72
647
5
1021
742
311
3900
7,2
2612
327
63
506
2
789
626
299
5
6300
6,9
4110
520
89
738
7
1390
1005
361
5530
7,06
4323
501
94
731
4
1599
1040
354
6
5080
6,95
3345
403
81
666
8
1160
661
366
3850
7,15
2832
363
66
499
5
953
598
348
7
5790
6,9
3630
560
115
550
4
1457
635
309
4740
7
3231
523
103
471
3
1181
633
317
8
3730
6,9
2306
286
115
284
20
895
377
329
3560
7,11
2407
353
135
294
12
876
421
317
9
5660
7,03
3800
368
129
881
11
1487
563
361
4660
7,16
3126
339
96
609
7
1248
498
329
10
3530
7,3
2384
249
59
388
25
788
589
287
2840
7,63
1989
258
46
347
20
610
489
220
11
4480
7,12
3260
379
72
646
18
989
820
337
3650
7,19
2674
334
59
500
13
774
683
311
12
3250
7
2142
230
55
346
37
705
477
293
3160
7,35
2360
285
55
434
37
720
543
287
13
2770
7
1658
216
45
264
31
474
352
277
2540
7,35
1710
243
41
262
29
487
380
268
14
2480
7,65
1972
278
46
337
24
659
382
246
2860
7,49
2040
263
50
343
23
662
462
238
15
6250
7,96
4089
466
86
857
96
1463
811
310
4230
7,35
3049
353
71
605
26
866
684
445
16
4190
7,6
2480
258
78
444
22
830
619
231
3520
7,38
2392
276
70
421
19
766
598
244
17
3990
7,5
2715
274
49
550
107
775
460
500
3290
7,7
2497
280
50
426
80
652
413
598
18
2920
7,2
2046
221
56
330
79
472
444
445
2240
7,29
1841
199
45
289
75
444
363
427
19
2730
7,75
1817
236
54
285
25
451
382
381
2250
7,3
1680
215
46
256
31
427
395
311
20
4020
7,23
2747
208
131
525
6
1011
481
386
3360
7,33
2389
206
124
410
3
872
384
390
21
1240
7,78
819
48
36
165
7
289
102
173
2120
7,55
1317
104
57
270
5
639
108
134
22
3280
7,05
2358
258
55
377
35
844
515
275
2910
7,65
1835
230
42
338
32
589
366
238
23
1573
7,68
924
84
19
200
6
276
89
250
1131
7,82
783
73
12
182
3
217
88
207
24
5170
7,15
2891
505
75
510
8
1185
407
201
4060
7,05
2697
490
67
433
5
1066
436
201
25
4610
7,3
2910
189
113
576
7
916
652
458
3880
7,33
2889
211
123
590
4
878
650
433
26
5050
7,3
2330
7,33
1666
216
55
270
12
464
264
387
27
3400
7,55
1938
255
65
287
27
594
415
296
2720
7,33
1928
257
62
312
35
568
371
323
28
3160
7,6
1662
178
48
289
87
478
356
226
2520
7,39
1910
279
57
280
16
593
393
293
29
2950
7,89
2176
187
66
419
6
713
587
198
30
3580
7,2
2353
199
80
437
11
819
613
195
3240
7,5
2217
205
72
427
11
732
582
189
31
3090
7,5
2187
225
71
394
10
710
560
217
3240
7,54
2330
228
68
424
7
766
637
201
32
3490
7,6
2317
231
69
479
10
749
560
221
3830
7,35
2804
269
80
572
7
866
723
287
33
4290
7,1
2886
358
70
404
20
954
729
351
5080
7,75
3608
454
90
654
23
1107
884
397
34
3640
7,25
2648
292
66
520
15
851
591
315
3410
7,35
2429
305
67
401
12
764
575
305
35
3860
7,25
2836
326
81
550
27
874
634
344
3420
7,51
2487
304
71
455
14
756
571
317
36
4820
7,95
3253
398
81
472
36
1084
789
393
4110
7,43
3015
348
74
539
38
922
729
366
37
3740
7,45
2390
230
78
412
17
829
607
218
3320
7,32
2441
265
70
474
16
757
609
250
38
2720
7,7
1881
197
55
332
9
591
465
232
3650
7,5
2628
292
71
491
6
821
654
293
39
2080
7,7
1378
169
32
251
11
470
336
110
1817
7,49
1269
158
30
213
8
391
319
153
40
3540
7,4
2454
231
75
419
8
823
620
278
3770
7,19
2727
273
81
489
7
865
696
317
41
5030
7,1
3010
402
81
456
14
1166
689
201
3130
7,67
2233
232
68
431
7
734
578
183
42
2820
7,93
2061
179
65
371
6
683
580
177
44
2980
7,12
1817
236
43
324
78
531
337
270
2090
7,52
1694
198
42
234
64
502
355
299
45
2670
7,1
1694
215
43
277
69
493
316
281
2130
7,4
1553
203
40
258
67
437
294
256
46
2840
7,4
1741
200
55
267
9
555
375
281
3050
7,3
2277
285
69
390
3
770
516
244
47
3310
7,05
1749
300
59
217
3
680
233
256
3170
7,3
2257
389
57
249
2
807
522
232
48
4990
7,06
2856
555
82
400
5
1210
355
250
4120
7,1
2601
560
73
327
2
1084
372
183
EC (μs/cm); TDS, Ca2+, Mg2+, Na+, K+, Cl−, SO42-, HCO3- (mg/l).Piper plots [34],considered as the common method for a multiple analyses on the same graph, are used to represent the different water samples and to distinguish graphically between different water types defined by the Stuyfzand classification (1993). Sample points with similar hydrochemistry tend to cluster together in the diagram [35].Principal component analysis method (PCA) and correlations are a popular method to assess groundwater quality. One of the principle advantages of multivariate techniques such as principal component analysis (PCA) is that they are able to rapidly reveal relationships between a large number of variables. In this study, PCA and correlations are used to identify the possible sources of major ions in groundwater, hydrogeological reactions that may occur in the study area, and dominant factors that control groundwater quality.Gibbs diagrams which are a simple plot of the TDS versus the weight ratio of Na+/(Na+ + Ca2+) or Cl-/(Cl-+HCO3-) are widely used to establish the relationships between the water composition and the lithological characteristics of the aquifer [36]. Three distinct fields, including precipitation dominance, evaporation dominance, and rock weathering dominance, constitute the segments in the Gibbs diagram.Hydrogeochemical Modeling. The equilibrium state of the water with respect to a mineral phase can be determined by calculating saturation index (SI) using analytical data. In this study, saturation indices (SI) were calculated in terms of the following equation [37]: (1)SI=log⁡IAPksT,where IAP is the relevant ion activity product, which can be calculated by multiplying the ion activity coefficientγi and the composition concentration mi, and ksT is the equilibrium constant of the reaction considered at the sample temperature [35]. The geochemical modeling program PHREEQC has been used to evaluate the water chemistry. SI>0 indicates oversaturation and minerals may be subject to precipitation, SI<0 means undersaturation and minerals will dissolve, and SI=0 suggests saturation and minerals are in equilibrium status with respect to the solution [38].


## 4. Results and Discussion

### 4.1. Hydrogeochemical Characterization

Groundwater quality depends on various chemical constituents and their concentrations, which are mostly derived from the geological stratum of the particular region [6]. The pH was one of the primary indicators of the water chemistry evolution. The aquifer groundwater was neutral to slightly alkaline water, with a mean pH value of 7,23 and 7,15 in the wet and dry season, respectively. Electrical conductivity (EC) of the water samples was medium to high, suggestive of very highly mineralized waters. EC values ranged between 1240 and 6300 μS/cm in the wet season and between 1131 and 5430 μS/cm in the dry season. A problem to the water supply development in the area is the increasing electrical conductivity (EC) values of near-coastal shallow groundwater. The high EC of groundwater from wells located along the coast and in Bahirat Beni Ata can be explained by the seawater intrusion effect caused by the groundwater level drawdown due to overexploitation (Figures 6(a) and 6(b)).Figure 6
Spatial distribution of electrical conductivity (a) wet season and (b) dry season in Ras Jbel aquifer.
(a)
(b)Based on the conductivity values, the groundwater system could be classified into four groups: fresh water (<500μS/cm), marginal water (500–1,500 μS/cm), brackish water (1,500–5,000 μS/cm), and saline water (>5,000 μS/cm). Based on our conductivity values it is evident that groundwater in Ras Jbel aquifer is in marginal and brackish waters. Few samples are of saline water type.The study area is characterized by a wide range of salinities. Salinity values ranged between 500 and 3600 mg/l in the wet season and between 500 and 3500 mg/l in the dry season. The higher values of EC and salinity are indicators of higher ionic concentrations, probably due to the high anthropogenic activities in the region and geological weathering conditions but also due to the intrusion of sea water into the groundwater system.The relative content of a cation or an anion is defined as the percentage of the relative amount of that ion to the total cations or anions, respectively [39]. In the study area, the strong acid anions (Cl− and SO42-) exceed weak acid anions (HCO3- and CO32-). On the other hand, sodium and calcium concentrations exceed magnesium and potassium contents. The triangular diagram (Figure 7) shows that the groundwater chemistry was mainly characterized by two groups. The first group was Cl-–Na+ type, in which Na+ accounted for more than 52–65% of the total cations; the second group was Cl-–Na+/Ca2+ type, in which Na+ and Ca2+ accounted for 37–48% and 36–53% of the total cations, respectively. Chemical facies in the phreatic aquifer of Ras Jbel seem to be directly related to the configuration of the ante-quaternary substratum and the proximity of several sampled wells from the sea.Figure 7
Piper diagram of groundwater: zone 1: alkaline earths (Ca + Mg) exceed alkalis (Na + K); zone 2: alkalis exceed alkaline earths; zone 3: weak acids (CO3 + HCO3) exceed strong acids (SO4 + Cl); zone 4: strong acids exceed weak acids; zone 5: carbonate hardness > 50% (alkaline earths and weak acid dominate); zone 6: noncarbonate hardness > 50%; zone 7: noncarbonate alkali > 50%; zone 8: carbonate alkali > 50% (groundwater is inordinately soft in proportion to the content of TDS); zone 9: no cation–anion pair >50% [34].The Na–Cl-type indicated the presence of high chloride concentrations in the aquifer which may originate from the dissolution of halite, influx of sewage or waste water, and mainly intrusion of sea water [40]. In the downstream part of the plain near the sea and in Bahirat Beni Ata, where a marine intrusion was detected since 1980, the groundwater is mainly of Cl-–Na+ type (Figure 8). The distribution maps of Cl− in both wet and dry seasons (Figures 9(a) and 9(b)) are well correlated with those of electrical conductivity and facies.Figure 8
Distribution map of the groundwater facies in the shallow aquifer of Ras Jbel.Figure 9
Spatial distribution of chlorides (a) wet season and (b) dry season in Ras Jbel aquifer.
(a)
(b)


### 4.2. Processes Controlling Groundwater Salinization

Understanding the water salinization mechanism is the basis for regional salt management. Groundwater salinization is largely a function of the mineral composition of the aquifer through which it flows and hydrogeochemical processes such as mineral dissolution, precipitation, evaporation and transpiration, ion exchange, and the residence time along the flow path. It is also linked to various anthropogenic activities such as agriculture, overexploitation of groundwater resources, and sewage disposal.


#### 4.2.1. Water-Rock Interaction and Origin of Groundwater Mineralization

Reactions between groundwater and aquifer minerals have a significant role on water quality. Thep×p correlation matrix, revealing the existence of bivariate linear correlations between variables, allows a better understanding of the dominant water-rock interactions or source of the ions over the study area. Additionally, the use of multivariate statistics in hydr(geo)logical studies is a very common practice and numerous applications can be found in the literature ([10, 19, 41]) though most hydrologists consider that values larger than 0.5 indicate significant correlation. In the present study, PCA was carried out for 10 parameters (Ca, Mg, Na, K, HCO3, SO4, Cl, pH, TDS, and EC) and more than 90 observations (Tables 2 and 3). The first two factors F1 and F2 were always retained, explaining about 73% of the total variance (Table 2). Factors of a higher order generally explained the variance of a single parameter or established poorer and less significant correlations with two parameters [42].Table 2
Principal component matrix.
F
1
F
2
F
3
CE
0,97
−0,03
0,05
TDS
0,98
−0,04
0,08
pH
−0,41
−0,42
0,75
Ca2+
0,82
0,17
−0,10
Mg2+
0,78
0,13
0,02
Na+
0,89
−0,20
0,17
K+
−0,11
−0,86
−0,16
Cl−
0,96
0,14
0,07
S
O
4
2
-
0,77
−0,20
0,28
H
C
O
3
-
0,43
−0,57
−0,49
Eigenvalue
5,86
1,40
0,95
% Explication
58,64
14
9,53
% Cumulative
58,64
72,64
82,17
Bold values: loadings ≥ 0.5.Table 3
Correlation matrix of dissolved species and the TDS for the study area in wet season.
CE
TDS
pH
Ca2+
Mg2+
Na+
K+
Cl−
S
O
4
2
-
H
C
O
3
-
CE
1
TDS
0,98
1
pH
−0,34
−0,32
1
Ca2+
0,84
0,83
−0,44
1
Mg2+
0,73
0,73
−0,30
0,43
1
Na+
0,84
0,87
−0,18
0,60
0,65
1
K+
−0,04
−0,05
0,23
−0,11
−0,28
0,01
1
Cl−
0,95
0,96
−0,37
0,84
0,76
0,84
−0,19
1
S
O
4
2
-
0,73
0,76
−0,12
0,50
0,52
0,75
−0,02
0,65
1
H
C
O
3
-
0,36
0,37
−0,20
0,20
0,37
0,42
0,30
0,27
0,32
1The correlations established between the TDS and concentrations of major elements (Table3) show that the TDS is well correlated with the concentrations of chloride (r2=0,96), sodium (r2=0,87), calcium (r2=0,83), magnesium (r2=0,73), and sulphates (r2=0,76). The high correlation of TDS with chloride, sodium, magnesium, sulphate, and calcium indicated that these elements are mostly contributed by mineralization. These ions have been dissolved into groundwater continuously and resulted in the rise of TDS. The contribution of carbonates and potassium is negligible (r2=0,37 and r2=-0,05, resp.). The low correlation between TDS and pH suggests that the dissolution of the salts is not related to acidic conditions of groundwater but it is related to their degrees of solubility. HCO3- and pH apparently have little association with the other variables.Bicarbonates are not correlated to calciumr(HCO3Ca) = 0,20 indicating another source other than the calcite dissolution. However, considerable correlation coefficients between sodium and chloridesr(NaCl) = 0,84 and between calcium and sulphatesr(CaSO4) = 0,50 suggest halite and gypsum dissolution, respectively.The first factorF1 accounts for 58% of the total variance, and it is contributed by the following variables: EC, TDS, Mg, Ca, Na, Cl, and SO4. This factor is associated with the salinity component (NaCl salt source with Ca and SO4 enrichment) and the cation exchange. The second factor F2 accounts for 14% of the total variance, and it is negatively determined by K and HCO3 (Figure 10). It suggests carbonates weathering and pollution by fertilizer application.Figure 10
Representation of variables into two principal factors:F1-F2 (a) and F1–F3 (b).
(a)
(b)In order to understand the origin of groundwater mineralization in Ras Jbel plain, the saturation index (SI) was calculated. The mineral facies are chosen based on the analysis result of groundwater quality, the main components of groundwater, and the occurrences conditions ([6, 43, 44]). In the study area, the main cations are Na+, Ca2+, and Mg2+ and the main anions are HCO3-, SO42-, and Cl−; thus gypsum, anhydrite, calcite, dolomite, aragonite, and halite are chosen to be the mineral facies.The positive values of the calculated SI with respect to calcite and dolomite for all groundwater samples (Figure11) suggest their oversaturation in respect to these minerals (0,05<SIcalcite<1,32 and 0,08<SIcalcite<1,18 in the wet and dry seasons, resp., and -0,10<SIdolomite<2,29 and 0,06<SIdolomite<1,98 in the wet and dry seasons, resp.). As described by Appelo and Postma [45], the dissolution of calcite and dolomite is as follows:Calcite:(2)CaCO3+CO2+H2O⟷Ca2++2HCO3-Dolomite:(3)CaMgCO32+2CO2+2H2O⟷Ca2++Mg2++4HCO3-However, focusing on the scatter plots of bicarbonate versus calcium and calcium + magnesium versus bicarbonate we notice that groundwater samples are not plotted on the 1 : 1 straight lines of calcite and dolomite dissolution (Figures 12(a) and 12(b)). Groundwater samples show an excess of Ca2+ that can be explained by the gypsum dissolution.Figure 11
Variation of saturation indices of selected minerals in wet and dry seasons.Figure 12
Water-rock interaction: relationships between different solutes of Na+, Ca2+, Mg2+, Cl−, SO42-, and HCO3- (a, b, c, d).
(a)
(b)
(c)
(d)The plot of SIGypsum and SIAnhydrite versus TDS exhibits a proportional and parabolic shape evolution with negative values of the saturation indexes (Figure11) (-1,86<SIgypsum<-0,34 and -1,72<SIgypsum<-0,35 in the wet and dry seasons, resp., and -2,08<SIanhydrite<-0,56 and -1,94<SIanhydrite<-0,56 in the wet and dry seasons, resp.). Thus, both calcium and sulphate are derived from the same origin, which is the dissolution of gypsum and anhydrite.(4)Gypsum:CaSO4·2H2O⟷Ca2++SO42-+2H2OHowever, the plot of sulphate versus calcium (Figure 12(c)) shows an excess of Ca2+ ions for the majority of the groundwater samples. For these samples, the (Ca/(Ca+SO4)) ionic ratio greater than 0,5 ratio (from 0,53 and 0,79) confirms the ionic exchange process [46]. The (Ca/(Ca+SO4)) ionic ratio close to 0,5 confirms that the main source of Ca2+ is the gypsum dissolution [46].A bivariate diagram of sodium versus chloride (Figure12(d)) reveals two main groups: for the first group halite dissolution was maintained for a slope equal to unity where majority of the samples are situated on the 1 : 1 straight of halite dissolution given by the following reactions [45]: (5)Halite:NaCl⟷Na++Cl-The second group includes the high-salinity samples (Na–Cl type), which do not follow the halite dissolution line and show enrichment in chloride compared to sodium. Thus, another phenomenon other than geological effect is controlling their salinization, and this may be the salt water intrusion.Water samples were plotted in the Gibbs diagrams, which takes into account the major role of natural mechanisms (rock weathering, evaporation, and precipitation). Figure13 clearly shows that the mechanism controlling water chemistry seems to be a combination of the weathering of carbonates minerals as well as the evaporation-precipitation processes. However, low rates of the groundwater samples were obtained in areas that were dominated by rock-water interactions.Figure 13
Gibbs diagram showing TDS versus (a) Na/(Na + Ca) and (b) Cl/(Cl + HCO3).
(a)
(b)Samples with Na+/(Na+ + Ca2+) or Cl−/(Cl− + HCO3-) ratios greater than 0,5 and TDS levels between 783 and 4323 mg/l showed that the groundwater chemistry was controlled mainly by the saline water mixing or evaporation. Evaporation results in increased TDS in relation to high ratios of dominant cations and anions and CaCO3 precipitates by losing Ca2+ and HCO3-.


#### 4.2.2. Ionic Exchange Processes and Freshwater-Saline Water Mixing

Ion exchange is one of the important natural processes responsible for the concentration of ions in groundwater and has significant impact on the evolution of groundwater chemistry [18]. The dominance of salty groundwater dominated by sodium and chloride ions in Ras Jbel shallow aquifer provides evidence of mixing with an external salinity source, which could be the seawater from the coastal part of the aquifer. Cation exchange, responsible for the salinity signature, is described by two mixing mechanisms (freshening and saline water intrusion). Equations (6) and (7) show the gain or loss related to Na+ and (Ca2+ + Mg2+) within the exchanger X.The freshening process or direct ion exchange: where Ca2+ from freshwater displaced the marine cations Na+ and Mg2+ from the exchanger complex. The resulting loss of Ca2+ from solution decreases the saturation state for calcite and possibly causes calcite dissolution.(6)12Ca2++Na–X⟶Na++12Ca–XThe intrusion of seawater or reverse ion exchange also triggered cation exchange reactions where Ca2+ was expelled from the exchanger by seawater Na+ and Mg2+. The released Ca2+ is being flushed from the aquifer by groundwater flow [45, 47].(7)12Na++Ca–X⟶Ca2++12Na–XThe plot of [(Ca2++Mg2+)–(HCO3-+SO42-)] versus (Na+–Cl−) determines the exchange of Na+ against (Ca2+ or Mg2+) through the clay matrix. The relationship [(Ca2+ + Mg2+)–(HCO3-+SO42-)] is the gain or loss of (Ca2+ + Mg2+) due to the carbonates and gypsum dissolution. The relationship of (Na+–Cl−) determines the gain or loss of Na+ relative to the halite dissolution. If there is no ion exchange, all water samples will be placed in the origin of diagram [46].Figure14 shows that reverse ion exchange is a dominant process. To confirm the effect of reverse ion exchange, chloroalkaline index CAI-1 was calculated in milliequivalents per liter according to the relationship proposed by Schoeller [48]: (8)CAI-1=Cl--Na++K+Cl-If reverse ion exchange occurs in groundwater, CAI-1 values are positive. The calculated CAI-1 values are positive for more than 70% of the water samples which confirmed that reverse ion exchange is a dominant process. This shows that the interaction between the seawater and groundwater in the study area is playing a major role in the contamination of the aquifer by seawater intrusion. These results indicate that seawater/freshwater interface is in a continuous evolution despite the artificial recharge operations since 1993, and this probably because of the permanent heavy pumping.Figure 14
Plot of[(Ca2++Mg2+)–(HCO3-+SO42-)] versus (Na+ + K+–Cl−) for ion exchange.Water samples concentrated in the origin of the plot[(Ca2++Mg2+)–(HCO3-+SO42-)] versus (Na+–Cl−) indicated the absence of the ion exchange process which can be attributed to the evaporation process followed by carbonate precipitation [49]. This result confirmed the results obtained using saturation states of minerals and Gibbs diagrams.The seawater fraction in the groundwater is often estimated using chloride concentration [50]. Chloride ion has been considered as a conservative tracer not affected by ion exchange [51]. For conservative mass balance of the mixture, the equation used is as follows [45]: (9)f=Clmix-ClfreshwaterClseawater-Clfreshwater×100,where Clmix is the Cl− concentration of the sample, Clseawater is the Cl− concentration of the Mediterranean Sea, and Clfreshwater represents the Cl− concentration of the fresh water. The fresh water sample will be chosen considering the lowest measured value of the electrical conductivity.The rate of mixture varies from 0,32% (well n°23) in the north of the Raf Raf region and where the configuration of the ante-quaternary substratum prevents the marine intrusion to 13% (well n°1) near the shoreline (close to the coast). The highest value of the mixing fraction corresponds to the highest measured values of Cl− and EC (1792 mg/l and 5430 μS/cm, resp.).


### 4.3. Isotopes and Groundwater Origin

The stable isotope ratios of oxygen and hydrogen in the groundwater are useful tools to differentiate between salinity origins [52, 53] and to help us understand various sources of recharge processes to groundwater because they are sensitive to physical processes such as atmospheric circulation, groundwater mixing, and evaporation ([33, 54]).In arid and semiarid regions evaporation could be an important process influencing groundwater chemistry [19]. To understand the relationship between isotopic composition of groundwater of the shallow aquifer of Ras Jbel and those of precipitation measured at the station of Tunis Carthage situated at 50 km from the plain of Metline-Ras Jbel- Raf Raf, a bivariate diagram δ2H versus δ18O is plotted in Figure 15(a).Figure 15
Isotopic relationships of groundwater in the study area.
(a)
(b)
(c)
(d)
(e)A local meteoric water line (LMWL) for Tunis Carthage was used to interpret the data in this study. The local meteoric water line (LMWL) is controlled by local hydrometeorological factors, including the origin of the vapor mass, reevaporation during rainfall, and the seasonality of precipitation [33]. The isotope composition of the precipitation was plotted along the LMWL using the following equation: δ2H (‰) = 8∗δ18O (‰) + 12,4 (which had a correlation coefficient R2=0,99) [55, 56].Figure15(a) shows that the isotopic composition of most of the groundwater samples collected in the wet season (except for sampling site number 35) lies within a narrow range, confirming that these groundwater samples had the same recharge source. Furthermore, all groundwater samples are scattered around the LMWL indicating that the recharge of the Ras Jbel shallow aquifer originates from infiltration of recent precipitation from Mediterranean vapor masses. Based on their isotopic composition, two groups of groundwater samples were identified (Table 4). The first group is relatively depleted in isotopic values and includes samples with δ18O and δ2H values ranging from −6,03 to −5,37‰ versus V-SMOW and from −33,94 to −29,66‰ versus V-SMOW, respectively. This may be explained by the fact that nonevaporated water is rapidly infiltrated to the saturated zone.Table 4
Isotopic data of sampled wells and piezometers in Ras Jbel aquifer.
Parameters
δ
18O (‰ versus SMOW)
δ
2H (‰ versus SMOW)
δ
18O (‰ versus SMOW)
δ
2H (‰ versus SMOW)
Wet season
Dry season
Minimum
−6,03
−33,94
−5,74
−31,46
Maximum
−3,5
−22,15
−0,06
−10,31
Average
−4,91
−28,06
−3,78
−23,33As per the second group, values vary from −5,35 to −3,50‰ versus V-SMOW and from −29,37 to −22,15‰ versus V-SMOW, for δ18O and δ2H, respectively. The relatively enriched isotopic values of the group 2 samples demonstrate that this groundwater is affected by evaporated open water or soil water.The groundwater samples collected in the dry season were enriched compared to those collected in the wet season. The results show isotopic content ranging from −5,74 to −0,06‰ versus V-SMOW for δ18O and from −31,46 to −10,31‰ versus V-SMOW for δ2H. This may be explained by heavy isotope enrichment in the groundwater caused by strong evaporation given that there was effectively no precipitation in the study area between the two sampling periods; meanwhile, the groundwater may have been mainly recharged by lateral inflow from outside the study area, resulting in seasonal fluctuations in the isotopic values. The enriched groundwater samples (n°15, 20, 25, 30, 32, 35, 38, 41, 45, and 48) might be an indicator for evaporation of the recharge water before its infiltration to the aquifer.The isotopic data for the groundwater collected in the wet season were linearly fit using the regression equationδ2H (‰) = 4,01∗δ18O (‰) − 8,37 (R2 = 0,82). This regression line can be interpreted as the groundwater evaporation line (GEL). The gel has a δ2H/δ18O slope <8, which reflects evaporation during or after rainfall and/or mixing with an external water source (e.g., return of irrigation water) with high δ18O and δ2H values. Furthermore, the GEL of the wet season intersected the LMWL at values of δ18O = −5,22‰ versus V-SMOW and δ2H = −29,37‰ versus V-SMOW. These values are estimated as baseline for δ2H and δ18O in recharging rainfall (Figures 15(b) and 15(c)). If samples are plotted above the lines, significant groundwater evaporation process can be confirmed.Additionally, the isotopic data from the dry season were linearly fit using the regression equationδ2H (‰) = 3,09∗δ18O (‰) − 11,81 (with a correlation coefficient R2 = 0,83). The GEL has a smaller slope than the LMWL, because evaporation tends to enrich heavy isotopes in water ([19, 57]). The increase in groundwater salinity due to evaporation can thus result in simultaneous increase in heavy isotopes ([19, 35]). The GEL of the dry season intersects the LMWL at values of δ18O = −4,93‰ versus V-SMOW and δ2H = −27,32‰ versus V-SMOW, which are chosen as baselines (Figures 15(d) and 15(e)). It is observed that 80% of the groundwater samples were plotted above the baselines and this demonstrates that evaporation has a significant contribution to groundwater salinity in the study area.Furthermore, the deuterium excess calculated as d-excess =δ2H − 8δ18O [54] has been widely used in hydrological studies. The d-excessis used to identify secondary processes that influence the atmospheric vapor content in the evaporation–condensation cycle in nature ([54, 58]). The d-excess plotted against δ18O shows a negative correlation for the whole set of samples (Figure 16). The decrease in d-excess is an indication that evaporation has occurred during the recharge process which again confirms the previous results.Figure 16
Plot of d-excess versusδ18O.


### 4.4. Irrigation Return Flow

Irrigation return flow is defined as the excess of irrigation water that is not evapotranspirated or evacuated by direct surface drainage and which returns to an aquifer or surface water [59, 60]. Irrigation return flows may induce salt and nitrate pollution of receiving water bodies [61]. Indeed, NO3- is the most common water contaminant, and NO3- pollution is increasing because the number of anthropogenic sources is increasing [26].71% of groundwater samples are contaminated by nitrates where the concentration exceeds the permissible value of 50 mg/l set by WHO [62]. The spatial distribution of nitrates (Figure 17) shows that high nitrate contents are observed especially in the upstream of Ras Jbel aquifer. Groundwater contamination by nitrate is due to the intensive use of nitrogen fertilizers (Ca(NO3)2, KNO3, and MgSO4). In recent years, the agricultural land area in Ras Jbel plain has increased and copious amounts of nitrogenous fertilizer have been used, which have increased the groundwater NO3- concentrations.Figure 17
Spatial distribution of nitrate concentrations in the shallow aquifer of Ras Jbel during the dry season.Furthermore, return flow from irrigation water also seems to contribute notably to the recharge process. Most of groundwater samples shows a correlation between NO3 and δ18O, reflecting the significant role of evaporated and contaminated irrigation water to the groundwater salinization (Figure 18(a)). Huge quantities of irrigation return flow elevated groundwater level, hence increasing evaporation and inducing salinization [63]. As highlighted in Figure 18(b), the contamination by return of irrigation water is observed in the shallower horizons (depth ≤ 13 m).Figure 18
Plots ofNO3- versus water table depth and δ18O versus NO3-.
(a)
(b)


## 4.1. Hydrogeochemical Characterization

Groundwater quality depends on various chemical constituents and their concentrations, which are mostly derived from the geological stratum of the particular region [6]. The pH was one of the primary indicators of the water chemistry evolution. The aquifer groundwater was neutral to slightly alkaline water, with a mean pH value of 7,23 and 7,15 in the wet and dry season, respectively. Electrical conductivity (EC) of the water samples was medium to high, suggestive of very highly mineralized waters. EC values ranged between 1240 and 6300 μS/cm in the wet season and between 1131 and 5430 μS/cm in the dry season. A problem to the water supply development in the area is the increasing electrical conductivity (EC) values of near-coastal shallow groundwater. The high EC of groundwater from wells located along the coast and in Bahirat Beni Ata can be explained by the seawater intrusion effect caused by the groundwater level drawdown due to overexploitation (Figures 6(a) and 6(b)).Figure 6
Spatial distribution of electrical conductivity (a) wet season and (b) dry season in Ras Jbel aquifer.
(a)
(b)Based on the conductivity values, the groundwater system could be classified into four groups: fresh water (<500μS/cm), marginal water (500–1,500 μS/cm), brackish water (1,500–5,000 μS/cm), and saline water (>5,000 μS/cm). Based on our conductivity values it is evident that groundwater in Ras Jbel aquifer is in marginal and brackish waters. Few samples are of saline water type.The study area is characterized by a wide range of salinities. Salinity values ranged between 500 and 3600 mg/l in the wet season and between 500 and 3500 mg/l in the dry season. The higher values of EC and salinity are indicators of higher ionic concentrations, probably due to the high anthropogenic activities in the region and geological weathering conditions but also due to the intrusion of sea water into the groundwater system.The relative content of a cation or an anion is defined as the percentage of the relative amount of that ion to the total cations or anions, respectively [39]. In the study area, the strong acid anions (Cl− and SO42-) exceed weak acid anions (HCO3- and CO32-). On the other hand, sodium and calcium concentrations exceed magnesium and potassium contents. The triangular diagram (Figure 7) shows that the groundwater chemistry was mainly characterized by two groups. The first group was Cl-–Na+ type, in which Na+ accounted for more than 52–65% of the total cations; the second group was Cl-–Na+/Ca2+ type, in which Na+ and Ca2+ accounted for 37–48% and 36–53% of the total cations, respectively. Chemical facies in the phreatic aquifer of Ras Jbel seem to be directly related to the configuration of the ante-quaternary substratum and the proximity of several sampled wells from the sea.Figure 7
Piper diagram of groundwater: zone 1: alkaline earths (Ca + Mg) exceed alkalis (Na + K); zone 2: alkalis exceed alkaline earths; zone 3: weak acids (CO3 + HCO3) exceed strong acids (SO4 + Cl); zone 4: strong acids exceed weak acids; zone 5: carbonate hardness > 50% (alkaline earths and weak acid dominate); zone 6: noncarbonate hardness > 50%; zone 7: noncarbonate alkali > 50%; zone 8: carbonate alkali > 50% (groundwater is inordinately soft in proportion to the content of TDS); zone 9: no cation–anion pair >50% [34].The Na–Cl-type indicated the presence of high chloride concentrations in the aquifer which may originate from the dissolution of halite, influx of sewage or waste water, and mainly intrusion of sea water [40]. In the downstream part of the plain near the sea and in Bahirat Beni Ata, where a marine intrusion was detected since 1980, the groundwater is mainly of Cl-–Na+ type (Figure 8). The distribution maps of Cl− in both wet and dry seasons (Figures 9(a) and 9(b)) are well correlated with those of electrical conductivity and facies.Figure 8
Distribution map of the groundwater facies in the shallow aquifer of Ras Jbel.Figure 9
Spatial distribution of chlorides (a) wet season and (b) dry season in Ras Jbel aquifer.
(a)
(b)


## 4.2. Processes Controlling Groundwater Salinization

Understanding the water salinization mechanism is the basis for regional salt management. Groundwater salinization is largely a function of the mineral composition of the aquifer through which it flows and hydrogeochemical processes such as mineral dissolution, precipitation, evaporation and transpiration, ion exchange, and the residence time along the flow path. It is also linked to various anthropogenic activities such as agriculture, overexploitation of groundwater resources, and sewage disposal.


### 4.2.1. Water-Rock Interaction and Origin of Groundwater Mineralization

Reactions between groundwater and aquifer minerals have a significant role on water quality. Thep×p correlation matrix, revealing the existence of bivariate linear correlations between variables, allows a better understanding of the dominant water-rock interactions or source of the ions over the study area. Additionally, the use of multivariate statistics in hydr(geo)logical studies is a very common practice and numerous applications can be found in the literature ([10, 19, 41]) though most hydrologists consider that values larger than 0.5 indicate significant correlation. In the present study, PCA was carried out for 10 parameters (Ca, Mg, Na, K, HCO3, SO4, Cl, pH, TDS, and EC) and more than 90 observations (Tables 2 and 3). The first two factors F1 and F2 were always retained, explaining about 73% of the total variance (Table 2). Factors of a higher order generally explained the variance of a single parameter or established poorer and less significant correlations with two parameters [42].Table 2
Principal component matrix.
F
1
F
2
F
3
CE
0,97
−0,03
0,05
TDS
0,98
−0,04
0,08
pH
−0,41
−0,42
0,75
Ca2+
0,82
0,17
−0,10
Mg2+
0,78
0,13
0,02
Na+
0,89
−0,20
0,17
K+
−0,11
−0,86
−0,16
Cl−
0,96
0,14
0,07
S
O
4
2
-
0,77
−0,20
0,28
H
C
O
3
-
0,43
−0,57
−0,49
Eigenvalue
5,86
1,40
0,95
% Explication
58,64
14
9,53
% Cumulative
58,64
72,64
82,17
Bold values: loadings ≥ 0.5.Table 3
Correlation matrix of dissolved species and the TDS for the study area in wet season.
CE
TDS
pH
Ca2+
Mg2+
Na+
K+
Cl−
S
O
4
2
-
H
C
O
3
-
CE
1
TDS
0,98
1
pH
−0,34
−0,32
1
Ca2+
0,84
0,83
−0,44
1
Mg2+
0,73
0,73
−0,30
0,43
1
Na+
0,84
0,87
−0,18
0,60
0,65
1
K+
−0,04
−0,05
0,23
−0,11
−0,28
0,01
1
Cl−
0,95
0,96
−0,37
0,84
0,76
0,84
−0,19
1
S
O
4
2
-
0,73
0,76
−0,12
0,50
0,52
0,75
−0,02
0,65
1
H
C
O
3
-
0,36
0,37
−0,20
0,20
0,37
0,42
0,30
0,27
0,32
1The correlations established between the TDS and concentrations of major elements (Table3) show that the TDS is well correlated with the concentrations of chloride (r2=0,96), sodium (r2=0,87), calcium (r2=0,83), magnesium (r2=0,73), and sulphates (r2=0,76). The high correlation of TDS with chloride, sodium, magnesium, sulphate, and calcium indicated that these elements are mostly contributed by mineralization. These ions have been dissolved into groundwater continuously and resulted in the rise of TDS. The contribution of carbonates and potassium is negligible (r2=0,37 and r2=-0,05, resp.). The low correlation between TDS and pH suggests that the dissolution of the salts is not related to acidic conditions of groundwater but it is related to their degrees of solubility. HCO3- and pH apparently have little association with the other variables.Bicarbonates are not correlated to calciumr(HCO3Ca) = 0,20 indicating another source other than the calcite dissolution. However, considerable correlation coefficients between sodium and chloridesr(NaCl) = 0,84 and between calcium and sulphatesr(CaSO4) = 0,50 suggest halite and gypsum dissolution, respectively.The first factorF1 accounts for 58% of the total variance, and it is contributed by the following variables: EC, TDS, Mg, Ca, Na, Cl, and SO4. This factor is associated with the salinity component (NaCl salt source with Ca and SO4 enrichment) and the cation exchange. The second factor F2 accounts for 14% of the total variance, and it is negatively determined by K and HCO3 (Figure 10). It suggests carbonates weathering and pollution by fertilizer application.Figure 10
Representation of variables into two principal factors:F1-F2 (a) and F1–F3 (b).
(a)
(b)In order to understand the origin of groundwater mineralization in Ras Jbel plain, the saturation index (SI) was calculated. The mineral facies are chosen based on the analysis result of groundwater quality, the main components of groundwater, and the occurrences conditions ([6, 43, 44]). In the study area, the main cations are Na+, Ca2+, and Mg2+ and the main anions are HCO3-, SO42-, and Cl−; thus gypsum, anhydrite, calcite, dolomite, aragonite, and halite are chosen to be the mineral facies.The positive values of the calculated SI with respect to calcite and dolomite for all groundwater samples (Figure11) suggest their oversaturation in respect to these minerals (0,05<SIcalcite<1,32 and 0,08<SIcalcite<1,18 in the wet and dry seasons, resp., and -0,10<SIdolomite<2,29 and 0,06<SIdolomite<1,98 in the wet and dry seasons, resp.). As described by Appelo and Postma [45], the dissolution of calcite and dolomite is as follows:Calcite:(2)CaCO3+CO2+H2O⟷Ca2++2HCO3-Dolomite:(3)CaMgCO32+2CO2+2H2O⟷Ca2++Mg2++4HCO3-However, focusing on the scatter plots of bicarbonate versus calcium and calcium + magnesium versus bicarbonate we notice that groundwater samples are not plotted on the 1 : 1 straight lines of calcite and dolomite dissolution (Figures 12(a) and 12(b)). Groundwater samples show an excess of Ca2+ that can be explained by the gypsum dissolution.Figure 11
Variation of saturation indices of selected minerals in wet and dry seasons.Figure 12
Water-rock interaction: relationships between different solutes of Na+, Ca2+, Mg2+, Cl−, SO42-, and HCO3- (a, b, c, d).
(a)
(b)
(c)
(d)The plot of SIGypsum and SIAnhydrite versus TDS exhibits a proportional and parabolic shape evolution with negative values of the saturation indexes (Figure11) (-1,86<SIgypsum<-0,34 and -1,72<SIgypsum<-0,35 in the wet and dry seasons, resp., and -2,08<SIanhydrite<-0,56 and -1,94<SIanhydrite<-0,56 in the wet and dry seasons, resp.). Thus, both calcium and sulphate are derived from the same origin, which is the dissolution of gypsum and anhydrite.(4)Gypsum:CaSO4·2H2O⟷Ca2++SO42-+2H2OHowever, the plot of sulphate versus calcium (Figure 12(c)) shows an excess of Ca2+ ions for the majority of the groundwater samples. For these samples, the (Ca/(Ca+SO4)) ionic ratio greater than 0,5 ratio (from 0,53 and 0,79) confirms the ionic exchange process [46]. The (Ca/(Ca+SO4)) ionic ratio close to 0,5 confirms that the main source of Ca2+ is the gypsum dissolution [46].A bivariate diagram of sodium versus chloride (Figure12(d)) reveals two main groups: for the first group halite dissolution was maintained for a slope equal to unity where majority of the samples are situated on the 1 : 1 straight of halite dissolution given by the following reactions [45]: (5)Halite:NaCl⟷Na++Cl-The second group includes the high-salinity samples (Na–Cl type), which do not follow the halite dissolution line and show enrichment in chloride compared to sodium. Thus, another phenomenon other than geological effect is controlling their salinization, and this may be the salt water intrusion.Water samples were plotted in the Gibbs diagrams, which takes into account the major role of natural mechanisms (rock weathering, evaporation, and precipitation). Figure13 clearly shows that the mechanism controlling water chemistry seems to be a combination of the weathering of carbonates minerals as well as the evaporation-precipitation processes. However, low rates of the groundwater samples were obtained in areas that were dominated by rock-water interactions.Figure 13
Gibbs diagram showing TDS versus (a) Na/(Na + Ca) and (b) Cl/(Cl + HCO3).
(a)
(b)Samples with Na+/(Na+ + Ca2+) or Cl−/(Cl− + HCO3-) ratios greater than 0,5 and TDS levels between 783 and 4323 mg/l showed that the groundwater chemistry was controlled mainly by the saline water mixing or evaporation. Evaporation results in increased TDS in relation to high ratios of dominant cations and anions and CaCO3 precipitates by losing Ca2+ and HCO3-.


### 4.2.2. Ionic Exchange Processes and Freshwater-Saline Water Mixing

Ion exchange is one of the important natural processes responsible for the concentration of ions in groundwater and has significant impact on the evolution of groundwater chemistry [18]. The dominance of salty groundwater dominated by sodium and chloride ions in Ras Jbel shallow aquifer provides evidence of mixing with an external salinity source, which could be the seawater from the coastal part of the aquifer. Cation exchange, responsible for the salinity signature, is described by two mixing mechanisms (freshening and saline water intrusion). Equations (6) and (7) show the gain or loss related to Na+ and (Ca2+ + Mg2+) within the exchanger X.The freshening process or direct ion exchange: where Ca2+ from freshwater displaced the marine cations Na+ and Mg2+ from the exchanger complex. The resulting loss of Ca2+ from solution decreases the saturation state for calcite and possibly causes calcite dissolution.(6)12Ca2++Na–X⟶Na++12Ca–XThe intrusion of seawater or reverse ion exchange also triggered cation exchange reactions where Ca2+ was expelled from the exchanger by seawater Na+ and Mg2+. The released Ca2+ is being flushed from the aquifer by groundwater flow [45, 47].(7)12Na++Ca–X⟶Ca2++12Na–XThe plot of [(Ca2++Mg2+)–(HCO3-+SO42-)] versus (Na+–Cl−) determines the exchange of Na+ against (Ca2+ or Mg2+) through the clay matrix. The relationship [(Ca2+ + Mg2+)–(HCO3-+SO42-)] is the gain or loss of (Ca2+ + Mg2+) due to the carbonates and gypsum dissolution. The relationship of (Na+–Cl−) determines the gain or loss of Na+ relative to the halite dissolution. If there is no ion exchange, all water samples will be placed in the origin of diagram [46].Figure14 shows that reverse ion exchange is a dominant process. To confirm the effect of reverse ion exchange, chloroalkaline index CAI-1 was calculated in milliequivalents per liter according to the relationship proposed by Schoeller [48]: (8)CAI-1=Cl--Na++K+Cl-If reverse ion exchange occurs in groundwater, CAI-1 values are positive. The calculated CAI-1 values are positive for more than 70% of the water samples which confirmed that reverse ion exchange is a dominant process. This shows that the interaction between the seawater and groundwater in the study area is playing a major role in the contamination of the aquifer by seawater intrusion. These results indicate that seawater/freshwater interface is in a continuous evolution despite the artificial recharge operations since 1993, and this probably because of the permanent heavy pumping.Figure 14
Plot of[(Ca2++Mg2+)–(HCO3-+SO42-)] versus (Na+ + K+–Cl−) for ion exchange.Water samples concentrated in the origin of the plot[(Ca2++Mg2+)–(HCO3-+SO42-)] versus (Na+–Cl−) indicated the absence of the ion exchange process which can be attributed to the evaporation process followed by carbonate precipitation [49]. This result confirmed the results obtained using saturation states of minerals and Gibbs diagrams.The seawater fraction in the groundwater is often estimated using chloride concentration [50]. Chloride ion has been considered as a conservative tracer not affected by ion exchange [51]. For conservative mass balance of the mixture, the equation used is as follows [45]: (9)f=Clmix-ClfreshwaterClseawater-Clfreshwater×100,where Clmix is the Cl− concentration of the sample, Clseawater is the Cl− concentration of the Mediterranean Sea, and Clfreshwater represents the Cl− concentration of the fresh water. The fresh water sample will be chosen considering the lowest measured value of the electrical conductivity.The rate of mixture varies from 0,32% (well n°23) in the north of the Raf Raf region and where the configuration of the ante-quaternary substratum prevents the marine intrusion to 13% (well n°1) near the shoreline (close to the coast). The highest value of the mixing fraction corresponds to the highest measured values of Cl− and EC (1792 mg/l and 5430 μS/cm, resp.).


## 4.2.1. Water-Rock Interaction and Origin of Groundwater Mineralization

Reactions between groundwater and aquifer minerals have a significant role on water quality. Thep×p correlation matrix, revealing the existence of bivariate linear correlations between variables, allows a better understanding of the dominant water-rock interactions or source of the ions over the study area. Additionally, the use of multivariate statistics in hydr(geo)logical studies is a very common practice and numerous applications can be found in the literature ([10, 19, 41]) though most hydrologists consider that values larger than 0.5 indicate significant correlation. In the present study, PCA was carried out for 10 parameters (Ca, Mg, Na, K, HCO3, SO4, Cl, pH, TDS, and EC) and more than 90 observations (Tables 2 and 3). The first two factors F1 and F2 were always retained, explaining about 73% of the total variance (Table 2). Factors of a higher order generally explained the variance of a single parameter or established poorer and less significant correlations with two parameters [42].Table 2
Principal component matrix.
F
1
F
2
F
3
CE
0,97
−0,03
0,05
TDS
0,98
−0,04
0,08
pH
−0,41
−0,42
0,75
Ca2+
0,82
0,17
−0,10
Mg2+
0,78
0,13
0,02
Na+
0,89
−0,20
0,17
K+
−0,11
−0,86
−0,16
Cl−
0,96
0,14
0,07
S
O
4
2
-
0,77
−0,20
0,28
H
C
O
3
-
0,43
−0,57
−0,49
Eigenvalue
5,86
1,40
0,95
% Explication
58,64
14
9,53
% Cumulative
58,64
72,64
82,17
Bold values: loadings ≥ 0.5.Table 3
Correlation matrix of dissolved species and the TDS for the study area in wet season.
CE
TDS
pH
Ca2+
Mg2+
Na+
K+
Cl−
S
O
4
2
-
H
C
O
3
-
CE
1
TDS
0,98
1
pH
−0,34
−0,32
1
Ca2+
0,84
0,83
−0,44
1
Mg2+
0,73
0,73
−0,30
0,43
1
Na+
0,84
0,87
−0,18
0,60
0,65
1
K+
−0,04
−0,05
0,23
−0,11
−0,28
0,01
1
Cl−
0,95
0,96
−0,37
0,84
0,76
0,84
−0,19
1
S
O
4
2
-
0,73
0,76
−0,12
0,50
0,52
0,75
−0,02
0,65
1
H
C
O
3
-
0,36
0,37
−0,20
0,20
0,37
0,42
0,30
0,27
0,32
1The correlations established between the TDS and concentrations of major elements (Table3) show that the TDS is well correlated with the concentrations of chloride (r2=0,96), sodium (r2=0,87), calcium (r2=0,83), magnesium (r2=0,73), and sulphates (r2=0,76). The high correlation of TDS with chloride, sodium, magnesium, sulphate, and calcium indicated that these elements are mostly contributed by mineralization. These ions have been dissolved into groundwater continuously and resulted in the rise of TDS. The contribution of carbonates and potassium is negligible (r2=0,37 and r2=-0,05, resp.). The low correlation between TDS and pH suggests that the dissolution of the salts is not related to acidic conditions of groundwater but it is related to their degrees of solubility. HCO3- and pH apparently have little association with the other variables.Bicarbonates are not correlated to calciumr(HCO3Ca) = 0,20 indicating another source other than the calcite dissolution. However, considerable correlation coefficients between sodium and chloridesr(NaCl) = 0,84 and between calcium and sulphatesr(CaSO4) = 0,50 suggest halite and gypsum dissolution, respectively.The first factorF1 accounts for 58% of the total variance, and it is contributed by the following variables: EC, TDS, Mg, Ca, Na, Cl, and SO4. This factor is associated with the salinity component (NaCl salt source with Ca and SO4 enrichment) and the cation exchange. The second factor F2 accounts for 14% of the total variance, and it is negatively determined by K and HCO3 (Figure 10). It suggests carbonates weathering and pollution by fertilizer application.Figure 10
Representation of variables into two principal factors:F1-F2 (a) and F1–F3 (b).
(a)
(b)In order to understand the origin of groundwater mineralization in Ras Jbel plain, the saturation index (SI) was calculated. The mineral facies are chosen based on the analysis result of groundwater quality, the main components of groundwater, and the occurrences conditions ([6, 43, 44]). In the study area, the main cations are Na+, Ca2+, and Mg2+ and the main anions are HCO3-, SO42-, and Cl−; thus gypsum, anhydrite, calcite, dolomite, aragonite, and halite are chosen to be the mineral facies.The positive values of the calculated SI with respect to calcite and dolomite for all groundwater samples (Figure11) suggest their oversaturation in respect to these minerals (0,05<SIcalcite<1,32 and 0,08<SIcalcite<1,18 in the wet and dry seasons, resp., and -0,10<SIdolomite<2,29 and 0,06<SIdolomite<1,98 in the wet and dry seasons, resp.). As described by Appelo and Postma [45], the dissolution of calcite and dolomite is as follows:Calcite:(2)CaCO3+CO2+H2O⟷Ca2++2HCO3-Dolomite:(3)CaMgCO32+2CO2+2H2O⟷Ca2++Mg2++4HCO3-However, focusing on the scatter plots of bicarbonate versus calcium and calcium + magnesium versus bicarbonate we notice that groundwater samples are not plotted on the 1 : 1 straight lines of calcite and dolomite dissolution (Figures 12(a) and 12(b)). Groundwater samples show an excess of Ca2+ that can be explained by the gypsum dissolution.Figure 11
Variation of saturation indices of selected minerals in wet and dry seasons.Figure 12
Water-rock interaction: relationships between different solutes of Na+, Ca2+, Mg2+, Cl−, SO42-, and HCO3- (a, b, c, d).
(a)
(b)
(c)
(d)The plot of SIGypsum and SIAnhydrite versus TDS exhibits a proportional and parabolic shape evolution with negative values of the saturation indexes (Figure11) (-1,86<SIgypsum<-0,34 and -1,72<SIgypsum<-0,35 in the wet and dry seasons, resp., and -2,08<SIanhydrite<-0,56 and -1,94<SIanhydrite<-0,56 in the wet and dry seasons, resp.). Thus, both calcium and sulphate are derived from the same origin, which is the dissolution of gypsum and anhydrite.(4)Gypsum:CaSO4·2H2O⟷Ca2++SO42-+2H2OHowever, the plot of sulphate versus calcium (Figure 12(c)) shows an excess of Ca2+ ions for the majority of the groundwater samples. For these samples, the (Ca/(Ca+SO4)) ionic ratio greater than 0,5 ratio (from 0,53 and 0,79) confirms the ionic exchange process [46]. The (Ca/(Ca+SO4)) ionic ratio close to 0,5 confirms that the main source of Ca2+ is the gypsum dissolution [46].A bivariate diagram of sodium versus chloride (Figure12(d)) reveals two main groups: for the first group halite dissolution was maintained for a slope equal to unity where majority of the samples are situated on the 1 : 1 straight of halite dissolution given by the following reactions [45]: (5)Halite:NaCl⟷Na++Cl-The second group includes the high-salinity samples (Na–Cl type), which do not follow the halite dissolution line and show enrichment in chloride compared to sodium. Thus, another phenomenon other than geological effect is controlling their salinization, and this may be the salt water intrusion.Water samples were plotted in the Gibbs diagrams, which takes into account the major role of natural mechanisms (rock weathering, evaporation, and precipitation). Figure13 clearly shows that the mechanism controlling water chemistry seems to be a combination of the weathering of carbonates minerals as well as the evaporation-precipitation processes. However, low rates of the groundwater samples were obtained in areas that were dominated by rock-water interactions.Figure 13
Gibbs diagram showing TDS versus (a) Na/(Na + Ca) and (b) Cl/(Cl + HCO3).
(a)
(b)Samples with Na+/(Na+ + Ca2+) or Cl−/(Cl− + HCO3-) ratios greater than 0,5 and TDS levels between 783 and 4323 mg/l showed that the groundwater chemistry was controlled mainly by the saline water mixing or evaporation. Evaporation results in increased TDS in relation to high ratios of dominant cations and anions and CaCO3 precipitates by losing Ca2+ and HCO3-.


## 4.2.2. Ionic Exchange Processes and Freshwater-Saline Water Mixing

Ion exchange is one of the important natural processes responsible for the concentration of ions in groundwater and has significant impact on the evolution of groundwater chemistry [18]. The dominance of salty groundwater dominated by sodium and chloride ions in Ras Jbel shallow aquifer provides evidence of mixing with an external salinity source, which could be the seawater from the coastal part of the aquifer. Cation exchange, responsible for the salinity signature, is described by two mixing mechanisms (freshening and saline water intrusion). Equations (6) and (7) show the gain or loss related to Na+ and (Ca2+ + Mg2+) within the exchanger X.The freshening process or direct ion exchange: where Ca2+ from freshwater displaced the marine cations Na+ and Mg2+ from the exchanger complex. The resulting loss of Ca2+ from solution decreases the saturation state for calcite and possibly causes calcite dissolution.(6)12Ca2++Na–X⟶Na++12Ca–XThe intrusion of seawater or reverse ion exchange also triggered cation exchange reactions where Ca2+ was expelled from the exchanger by seawater Na+ and Mg2+. The released Ca2+ is being flushed from the aquifer by groundwater flow [45, 47].(7)12Na++Ca–X⟶Ca2++12Na–XThe plot of [(Ca2++Mg2+)–(HCO3-+SO42-)] versus (Na+–Cl−) determines the exchange of Na+ against (Ca2+ or Mg2+) through the clay matrix. The relationship [(Ca2+ + Mg2+)–(HCO3-+SO42-)] is the gain or loss of (Ca2+ + Mg2+) due to the carbonates and gypsum dissolution. The relationship of (Na+–Cl−) determines the gain or loss of Na+ relative to the halite dissolution. If there is no ion exchange, all water samples will be placed in the origin of diagram [46].Figure14 shows that reverse ion exchange is a dominant process. To confirm the effect of reverse ion exchange, chloroalkaline index CAI-1 was calculated in milliequivalents per liter according to the relationship proposed by Schoeller [48]: (8)CAI-1=Cl--Na++K+Cl-If reverse ion exchange occurs in groundwater, CAI-1 values are positive. The calculated CAI-1 values are positive for more than 70% of the water samples which confirmed that reverse ion exchange is a dominant process. This shows that the interaction between the seawater and groundwater in the study area is playing a major role in the contamination of the aquifer by seawater intrusion. These results indicate that seawater/freshwater interface is in a continuous evolution despite the artificial recharge operations since 1993, and this probably because of the permanent heavy pumping.Figure 14
Plot of[(Ca2++Mg2+)–(HCO3-+SO42-)] versus (Na+ + K+–Cl−) for ion exchange.Water samples concentrated in the origin of the plot[(Ca2++Mg2+)–(HCO3-+SO42-)] versus (Na+–Cl−) indicated the absence of the ion exchange process which can be attributed to the evaporation process followed by carbonate precipitation [49]. This result confirmed the results obtained using saturation states of minerals and Gibbs diagrams.The seawater fraction in the groundwater is often estimated using chloride concentration [50]. Chloride ion has been considered as a conservative tracer not affected by ion exchange [51]. For conservative mass balance of the mixture, the equation used is as follows [45]: (9)f=Clmix-ClfreshwaterClseawater-Clfreshwater×100,where Clmix is the Cl− concentration of the sample, Clseawater is the Cl− concentration of the Mediterranean Sea, and Clfreshwater represents the Cl− concentration of the fresh water. The fresh water sample will be chosen considering the lowest measured value of the electrical conductivity.The rate of mixture varies from 0,32% (well n°23) in the north of the Raf Raf region and where the configuration of the ante-quaternary substratum prevents the marine intrusion to 13% (well n°1) near the shoreline (close to the coast). The highest value of the mixing fraction corresponds to the highest measured values of Cl− and EC (1792 mg/l and 5430 μS/cm, resp.).


## 4.3. Isotopes and Groundwater Origin

The stable isotope ratios of oxygen and hydrogen in the groundwater are useful tools to differentiate between salinity origins [52, 53] and to help us understand various sources of recharge processes to groundwater because they are sensitive to physical processes such as atmospheric circulation, groundwater mixing, and evaporation ([33, 54]).In arid and semiarid regions evaporation could be an important process influencing groundwater chemistry [19]. To understand the relationship between isotopic composition of groundwater of the shallow aquifer of Ras Jbel and those of precipitation measured at the station of Tunis Carthage situated at 50 km from the plain of Metline-Ras Jbel- Raf Raf, a bivariate diagram δ2H versus δ18O is plotted in Figure 15(a).Figure 15
Isotopic relationships of groundwater in the study area.
(a)
(b)
(c)
(d)
(e)A local meteoric water line (LMWL) for Tunis Carthage was used to interpret the data in this study. The local meteoric water line (LMWL) is controlled by local hydrometeorological factors, including the origin of the vapor mass, reevaporation during rainfall, and the seasonality of precipitation [33]. The isotope composition of the precipitation was plotted along the LMWL using the following equation: δ2H (‰) = 8∗δ18O (‰) + 12,4 (which had a correlation coefficient R2=0,99) [55, 56].Figure15(a) shows that the isotopic composition of most of the groundwater samples collected in the wet season (except for sampling site number 35) lies within a narrow range, confirming that these groundwater samples had the same recharge source. Furthermore, all groundwater samples are scattered around the LMWL indicating that the recharge of the Ras Jbel shallow aquifer originates from infiltration of recent precipitation from Mediterranean vapor masses. Based on their isotopic composition, two groups of groundwater samples were identified (Table 4). The first group is relatively depleted in isotopic values and includes samples with δ18O and δ2H values ranging from −6,03 to −5,37‰ versus V-SMOW and from −33,94 to −29,66‰ versus V-SMOW, respectively. This may be explained by the fact that nonevaporated water is rapidly infiltrated to the saturated zone.Table 4
Isotopic data of sampled wells and piezometers in Ras Jbel aquifer.
Parameters
δ
18O (‰ versus SMOW)
δ
2H (‰ versus SMOW)
δ
18O (‰ versus SMOW)
δ
2H (‰ versus SMOW)
Wet season
Dry season
Minimum
−6,03
−33,94
−5,74
−31,46
Maximum
−3,5
−22,15
−0,06
−10,31
Average
−4,91
−28,06
−3,78
−23,33As per the second group, values vary from −5,35 to −3,50‰ versus V-SMOW and from −29,37 to −22,15‰ versus V-SMOW, for δ18O and δ2H, respectively. The relatively enriched isotopic values of the group 2 samples demonstrate that this groundwater is affected by evaporated open water or soil water.The groundwater samples collected in the dry season were enriched compared to those collected in the wet season. The results show isotopic content ranging from −5,74 to −0,06‰ versus V-SMOW for δ18O and from −31,46 to −10,31‰ versus V-SMOW for δ2H. This may be explained by heavy isotope enrichment in the groundwater caused by strong evaporation given that there was effectively no precipitation in the study area between the two sampling periods; meanwhile, the groundwater may have been mainly recharged by lateral inflow from outside the study area, resulting in seasonal fluctuations in the isotopic values. The enriched groundwater samples (n°15, 20, 25, 30, 32, 35, 38, 41, 45, and 48) might be an indicator for evaporation of the recharge water before its infiltration to the aquifer.The isotopic data for the groundwater collected in the wet season were linearly fit using the regression equationδ2H (‰) = 4,01∗δ18O (‰) − 8,37 (R2 = 0,82). This regression line can be interpreted as the groundwater evaporation line (GEL). The gel has a δ2H/δ18O slope <8, which reflects evaporation during or after rainfall and/or mixing with an external water source (e.g., return of irrigation water) with high δ18O and δ2H values. Furthermore, the GEL of the wet season intersected the LMWL at values of δ18O = −5,22‰ versus V-SMOW and δ2H = −29,37‰ versus V-SMOW. These values are estimated as baseline for δ2H and δ18O in recharging rainfall (Figures 15(b) and 15(c)). If samples are plotted above the lines, significant groundwater evaporation process can be confirmed.Additionally, the isotopic data from the dry season were linearly fit using the regression equationδ2H (‰) = 3,09∗δ18O (‰) − 11,81 (with a correlation coefficient R2 = 0,83). The GEL has a smaller slope than the LMWL, because evaporation tends to enrich heavy isotopes in water ([19, 57]). The increase in groundwater salinity due to evaporation can thus result in simultaneous increase in heavy isotopes ([19, 35]). The GEL of the dry season intersects the LMWL at values of δ18O = −4,93‰ versus V-SMOW and δ2H = −27,32‰ versus V-SMOW, which are chosen as baselines (Figures 15(d) and 15(e)). It is observed that 80% of the groundwater samples were plotted above the baselines and this demonstrates that evaporation has a significant contribution to groundwater salinity in the study area.Furthermore, the deuterium excess calculated as d-excess =δ2H − 8δ18O [54] has been widely used in hydrological studies. The d-excessis used to identify secondary processes that influence the atmospheric vapor content in the evaporation–condensation cycle in nature ([54, 58]). The d-excess plotted against δ18O shows a negative correlation for the whole set of samples (Figure 16). The decrease in d-excess is an indication that evaporation has occurred during the recharge process which again confirms the previous results.Figure 16
Plot of d-excess versusδ18O.


## 4.4. Irrigation Return Flow

Irrigation return flow is defined as the excess of irrigation water that is not evapotranspirated or evacuated by direct surface drainage and which returns to an aquifer or surface water [59, 60]. Irrigation return flows may induce salt and nitrate pollution of receiving water bodies [61]. Indeed, NO3- is the most common water contaminant, and NO3- pollution is increasing because the number of anthropogenic sources is increasing [26].71% of groundwater samples are contaminated by nitrates where the concentration exceeds the permissible value of 50 mg/l set by WHO [62]. The spatial distribution of nitrates (Figure 17) shows that high nitrate contents are observed especially in the upstream of Ras Jbel aquifer. Groundwater contamination by nitrate is due to the intensive use of nitrogen fertilizers (Ca(NO3)2, KNO3, and MgSO4). In recent years, the agricultural land area in Ras Jbel plain has increased and copious amounts of nitrogenous fertilizer have been used, which have increased the groundwater NO3- concentrations.Figure 17
Spatial distribution of nitrate concentrations in the shallow aquifer of Ras Jbel during the dry season.Furthermore, return flow from irrigation water also seems to contribute notably to the recharge process. Most of groundwater samples shows a correlation between NO3 and δ18O, reflecting the significant role of evaporated and contaminated irrigation water to the groundwater salinization (Figure 18(a)). Huge quantities of irrigation return flow elevated groundwater level, hence increasing evaporation and inducing salinization [63]. As highlighted in Figure 18(b), the contamination by return of irrigation water is observed in the shallower horizons (depth ≤ 13 m).Figure 18
Plots ofNO3- versus water table depth and δ18O versus NO3-.
(a)
(b)


## 5. Conclusions

This paper aimed to discuss the origin, processes, and mechanisms of groundwater salinization, as well as the chemical evolution of groundwater in the Ras Jbel coastal aquifer using isotopic tools and hydrochemical tracers.Most of the groundwater is considered to be of brackish to saline water and contains high ion concentrations. The groundwater in the study area is influenced by both natural and anthropogenic factors. The major geochemical processes controlling hydrochemical evolution are the inverse cationic exchange due to the phenomena of seawater intrusion, dissolution of evaporates minerals (halite, gypsum, and/or anhydrite), irrigation return flow, water-rock interactions, and evapo(transpi)ration. (Figure19). The mixing rate among freshwater and saline water ranges between 1 and 13%.Figure 19
Schematic conceptual model summarizing salinization sources of groundwater in the plain of Ras Jbel.In addition, groundwater in the shallow aquifer of Ras Jbel is also contaminated by agricultural fertilizers containing high amounts of nitrates. Nitrates are transported to the aquifer by natural recharge process and by return flow from irrigation water.Hydrogen and oxygen-18 stable isotopes signatures of groundwater have identified recent groundwater recharge by infiltration of local precipitations. The enrichment in stable isotope of groundwater confirms that return flow of irrigation waters is an important factor influencing groundwater quality.The results of this study can be used to improve our understanding of hydrogeochemical processes and enable the protection and sustainable use of water resources. It, therefore, calls for more comprehensive research for better water resources management.



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*Source: 8610894-2017-05-08.xml*