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Multivariate analysis and geochemical investigations of groundwater in a semi-arid region, case of superficial aquifer in Ghriss Basin, Northwest Algeria
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Abstract: This study aims to investigate the hydrochemical characteristics of shallow aquifer in a semi-arid region situated in northwest Algeria, and to understand the major factors governing groundwater quality. The study area is suffering from recurring droughts, groundwater resource over-exploitation and groundwater quality degradation. The approach used is a combination of traditional hydrochemical analysis methods of multivariate statistical techniques, principal component analysis (PCA), and ratios of major ions, based on the data derived from 33 groundwater samples collected in February 2014. Results show that groundwater in the study area are highly mineralized and collectively has a high concentration of chloride (as Cl−). The dominant water types are Na-Cl (27%), Mg-HCO3 (24%) and Mg-Cl (24%). According to the (PCA) approach, salinization is the main process that controls the hydrochemical variability. The PCA analysis reveal the impact of anthropogenic factor especially the agricultural activities on the groundwater quality. The PCA highlighted two types of recharge: Superficial recharge from effective rainfall and excess irrigation water distinguished by the presence of nitrate and lateral recharge or vertical leakage from carbonate formations marked by the omnipresence of HCO3−. Additionally, three categories of samples were identified: (1) samples characterized by good water quality and receiving notable recharge from carbonate formations; (2) samples impacted by the natural salinization process; and (3) samples contaminated by anthropogenic activities. The major natural processes influencing water chemistry are the weathering of carbonate and silicate rocks, dissolution of evaporite as halite, evaporation and cation exchange. The study results can provide the basis for local decision makers to ensure the sustainable management of groundwater and the safety of drinking water.
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Figure 1. Geological and piezometric map of the study area and groundwater samples location (Adapted from Sourisseau, 1972)
Figure 2. Lithologic correlation of borehole logs from the study area (Bekkoussa, 2009)
Figure 6. Gibbs plots illustrating main mechanisms impacting groundwater composition in the superficial aquifer in Ghriss plain
Figure 8. Bivariate plots of (a) (Ca2+ /Na2+) vs (Mg2+/Na2+) and (b) (Ca2+ /Na2+) vs (HCO3− /Na2+)
Table 1. Lithostratigraphic units in the study area
Stratigraphic unit Lithology (thickness) Quaternary Alluvium (less than 100 m) Pliocene Astien sandstone and lacustrine limestones (40 m to 270 m). More clayed in upper part. Miocene Green marl (up to 400 m) Oligocene Clay-marly formations with sandstone passages (less than 100 m) Eocene Alternation of sandstone and clay-marly layers (less than 50 m) Lower Cretaceous Sandstone, limestones, and fine clayey sandstone at depth (up to 100 m) Jurassic (Kimmeridgian and Purbeckian) Graylimestones and dolomitic limestones (more than 400 m) Lusitano Sandstone and dolomitic benches (more than 150 m) Callovo- Oxfordian Clays and marls with alternating sandstone (more than 250 m) Trias Detritic formations and lagoon deposits rich in gypsum and halite 
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Table 2. Physicochemical parameters of groundwater samples
Well Ca2+
(mg/L)Mg2+
(mg/L)Na+
(mg/L)K+
(mg/L)Cl−
(mg/L)SO42−
(mg/L)HCO3−
(mg/L)NO3−
(mg/L)pH EC(25°C)
(μs/cm)TDS
(mg/L)P1 48 120 396 2 634 164 465 9 8.51 2600 1 980 P2 87 190 322 4 839 235 399 18 7.79 3090 2 700 P3 110 57 71 2 123 110 379 7 7.76 960 700 P4 60 222 331 4 819 242 399 20 7.75 3130 2 700 P5 40 62 39 3 102 61 290 17 7.8 775 620 P6 108 259 423 2 1261 344 213 6 7.43 4040 3 680 P7 87 185 285 5 845 190 293 11 7.88 2890 2 500 P8 116 57 23 2 67 118 403 9 7.55 782 700 P9 40 72 154 4 273 99 253 11 7.67 1350 1 080 P10 87 58 255 4 320 266 353 5 7.88 1486 1 260 P11 100 62 230 8 402 121 279 60 8.05 1800 1 500 P12 164 93 182 9 600 90 213 72 8.3 2220 1 700 P13 120 47 138 4 293 95 319 55 8.22 1403 1 100 P14 114 58 28 2 55 109 419 17 7.91 786 580 P15 108 26 92 2 191 107 253 12 8.28 1090 900 P16 132 73 145 7 402 140 206 102 8 1810 1500 P17 120 77 150 4 382 132 273 44 7.93 1780 1500 P18 112 58 136 5 279 138 312 55 8.17 1417 1100 P19 277 127 345 4 1097 120 293 61 7.95 3660 2900 P20 84 45 92 2 211 124 239 13 8.11 1130 800 P21 60 74 51 2 150 18 366 18 8.04 930 720 P22 68 70 50 3 130 104 323 17 7.6 879 767 P23 87 75 107 4 328 100 245 18 7.6 1355 1223 P24 92 76 99 3 286 93 289 35 7.6 1408 1227 P25 51 60 58 2 157 70 268 15 7.44 821 860 P26 44 72 25 2 102 67 342 15 7.18 838 880 P27 60 50 55 3 109 80 336 9 7.52 860 560 P28 148 58 81 5 320 140 268 16 7.25 1370 1100 P29 120 113 288 7 518 119 617 21 7.1 2240 1660 P30 64 91 44 3 89 132 497 8 7.16 941 860 P31 82 88 91 6 193 131 398 45 7.3 1242 1030 P32 100 108 145 4 464 119 242 20 7.25 1730 1300 P33 92 64 60 3 136 83 443 9 7.3 980 900
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Table 3. Statistical summary of chemical parameters of groundwater samples (Units in mg/L, except EC (μs/cm))
Variable WHO standards Algerian standards Values in the aquifer of Ghriss basin Min Max Average St. Dev. Ca2+ 200 200 40 277 96 45 Mg2+ 150 150 26 259 89 53 Na+ 200 200 23 423 151 116 K+ 12 20 2 9 4 2 Cl− 250 500 55 1261 369 306 SO42− 250 400 18 344 129 64 HCO3− - - 206 617 330 92 NO3− 50 50 5 102 26 23 pH 6.5-9.2 <9.0 7.1 8.5 7.7 0.4 EC 1500 2800 775 4040 1630 887 TDS 1000 2000 560 3680 1351 761
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Table 4. Pearson correlation matrix of major physicochemical parameters in groundwater
Variables Ca2+ Mg2+ Na+ K+ Cl− SO42− HCO3− NO3− PH EC Ca2+ 1.00 Mg2+ 0.05 1.00 Na+ 0.26 0.77 1.00 K+ 0.36 0.07 0,27 1.00 Cl− 0.42 0.86 0.92 0.26 1.00 SO42− 0.08 0.73 0.74 0.05 0.69 1.00 HCO3− −0.18 0.07 0.05 −0.10 −0.15 −0.01 1.00 NO3− 0.54 −0.10 0.10 0.70 0.17 −0.14 −0.34 1.00 PH 0.18 −0.12 0.25 0.09 0.15 0.01 −0.29 0.38 1.00 EC 0.41 0.86 0.94 0.28 0.99 0.71 −0.07 0.19 0.17 1.00 NB: Values in bold correspond for coefficients greater than 0.5.
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Table 5. Principal component loadings and eigenvalues of the factor analysis
F1 F2 F3 Ca2+ 0.418 0.583 −0.192 Mg2+ 0.843 −0.412 −0.052 Na+ 0.940 −0.116 0.033 K+ 0.346 0.627 −0.506 Cl− 0.979 −0.036 0.044 SO42− 0.768 −0.365 0.100 HCO3− −0.103 −0.485 −0.593 NO3− 0.239 0.886 −0.163 PH 0.197 0.485 0.633 EC 0.988 −0.045 0.001 Eigenvalues 4.52 2.31 1.09 Explained variance (%) 45.22 23.09 10.88 Cumulative % of variance 45.22 68.31 79.19
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