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HYDROLOGICAL PROCESSES Hydrol. Process. 22, 611 622 (2008) Published online 4 June 2007 in Wiley InterScience (www.interscience.wiley.

com) DOI: 10.1002/hyp.6627

The role of bromide and iodide ions in the salinization mapping of the aquifer of Glafkos River basin (northwest Achaia, Greece)
D. Mandilaras,1 N. Lambrakis1 * and G. Stamatis2
2 1 Laboratory of Hydrogeology, Department of Geology, University of Patras, GR-265 00 Patras, Greece Agricultural University of Athens, Institute of Mineralogy-Geology, Iera Odos 75, GR-118 55 Athens, Greece

Abstract:
Seawater intrusion causes many problems for groundwater quality, whereas natural remediation is time consuming. However, in cases where groundwater replenishment is feasible, groundwater quality remediation is possible and rapid. The alluvial aquifer in the lowland of the Glafkos River basin, which extends south of Patras city, was for over 30 years the major water source supplying the broader area. Groundwater quality has been degraded due to seawater intrusion, caused by overpumping and generally by inappropriate groundwater management. During the last decade, groundwater quality has been remedied due to diminished groundwater abstractions. The remediation rate was further higher because of rapid discharge of the brackish groundwater, through wells with freely owing water in the coastal area, where, however, groundwater quality remains low. This paper deals with the hydrogeochemical processes that take place in the area. It is ascertained that ion exchange and mineral dilution processes are dominant. The ion relations between chloride, bromide and iodide, as well as the distribution maps of their concentrations, were used to determine the spatial distribution of the seawater intrusion front. In the lower part of the area in a distance from 1000 and 1500 m from the coast, the rBr /rCl ratio showed low values (<25 10 3 ) similar to those of seawater. The rI /rCl ratio also presented low values (<7 10 5 ), with the lowest one (27 10 5 ) detected along the coastline. In the upper part of the area, a gradual change of those ratios was observed upstream, until they receive values similar to those of the surface waters of Glafkos River. Copyright 2007 John Wiley & Sons, Ltd.
KEY WORDS

seawater intrusion; bromide; iodide; groundwater quality remediation

Received 23 May 2006; Accepted 6 November 2006

INTRODUCTION During recent decades, the continuously growing water demands in Patras, which is the third biggest city in Greece, were mainly satised from groundwater of the Glafkos River basin. Since the 1970s decade, intense exploitation combined with extended dry periods (19891992) and inappropriate water management has resulted in quantity reduction and quality degradation of the alluvial aquifer (Lambrakis et al., 1997; Mandilaras and Voudouris, 2001). Especially during 19911992, a signicant water level decline of the aquifer was observed. The conned conditions became unconned and a negative groundwater gradient occurred, from the sea towards inland, caused by sea intrusion to a 3 km distance from the coastline (Lambrakis et al., 1997). This was conrmed by the rapid increase in Cl concentration, which in several boreholes in the coastal area was greater than 4000 mg l 1 . Similar phenomena have also been mentioned for others Greek areas, such as the coastal plain of Rodope in northern Greece (Petalas, 1997), and the Argos plain, Peloponnese, southern Greece (Lambrakis, 2006).
* Correspondence to: N. Lambrakis, Section of Applied Geology and Geophysics, Department of Geology, University of Patras, 265 00 RioPatras, Greece. E-mail: nlambrakis@upatras.gr Copyright 2007 John Wiley & Sons, Ltd.

Since 1994, pumping of the municipal water-supply boreholes in the coastal area has been suspended. This, along with the transfer of the industries to the Industrial Area of Patras, has led to the inversion of the adverse impacts. Thus, since 1997, a signicant improvement of groundwater quality has been observed (Mandilaras and Voudouris, 2001) (Figure 1), as well as a reappearance of artesian phenomena. Additionally, great amounts of brackish groundwater from the coastal part of the aquifer (32 106 m3 year 1 ), discharges to the sea through several boreholes with freely owing water (artesian ow) allowing a rapid replenishment and leading to further improvement. Chemical element ratios are usually used to identify the origin of groundwater saline fraction in coastal aquifers. The classic Revelle criterion is one of them. The rCa/rMg ratio is also used in deltaic plains, since it is reduced along the groundwater ow direction to the sea (Stournaras, 1984). Because cations are involved in ion-exchange processes, chemical elements considered as relatively inert are preferred for the composition of these ratios. Bromide is an ion that shows increased concentration in saline waters. According to Sanders (1991) and Richter and Kreitler (1993), bromide is concentrated to the remaining solute phase during the evaporation of saline waters. It is considered as inert in relation to other

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D. MANDILARAS, N. LAMBRAKIS AND G. STAMATIS

Figure 1. Diagram of Cl ion variation in municipal water-supply borehole in the coastal part of the alluvial aquifer during the period 1988 2002 (Mandilaras, 2005)

ions and the rCl /rBr ratio is used for the study of the evolution of degree of salinity of waters (Whittemore, 1995; Edmunds, 1996; Dror et al., 1999). It is also used to identify the genesis of deep saline waters (Stober and Bucher, 1999). From this point of view, Davis et al. (1998) extensively revised the use of the rCl /rBr ratio in groundwater studies. The difference between its content in fresh and seawater, along with its low chemical activity, means that bromide is a reliable indicator of marine intrusion. Areas affected by seawater intrusion present similar rBr /rCl values to seawater, since both ions share a common origin. Therefore, in the case of absence of other factors affecting its concentration, Br can be successfully used to characterize seawater intrusion (Morell et al., 1986). In this paper, the hydrochemical processes in the Glafkoss alluvial aquifer are investigated as mixtures of fresh and seawater, mineral dissolution and ion exchanges. The extent of the seawater intrusion zone is also examined with the use of the ion ratios and distribution maps of Cl , Br and I . GEOLOGICALHYDROGEOLOGICAL SETTING OF THE STUDY AREA Glafkos River basin is located southeast of Patras city (Peloponnesus, southern Greece). The basin covers a surface of 102 km2 with a mean altitude of 810 m. The river network is moderately developed, characterized by the vertical opening of symmetric valleys, which are highly controlled by the pre-existing fault system. Based on the statistically elaborated data of ve meteorological stations located at different elevations of the basin wider area, the mean annual precipitation at sea level was 643 mm for the period 19751993, increasing with altitude at a rate of 491 mm per 100 m. For the same period, the mean annual precipitation of the whole basin was 1071 mm. The mean annual temperature was estimated at 126 C, decreasing with altitude at a rate of 066 C per 100 m. During recent decades, two extended
Copyright 2007 John Wiley & Sons, Ltd.

droughts affected the region, the rst during 19891992 and the second in 2000, leading to a reduction of the alluvial aquifer recharge (Mandilaras, 2005). The mountainous part of the basin (altitude >200 m a.s.l.) occupies an area of 85 km2 and belongs to the Pindos geotectonic zone, including limestones with radiolarites and ysh intercalations. The ysh formation consists of alternations of sandstones and siltstones with conglomerate intercalations (Tsoias, 1970; Doutsos et al., 1987). Post-alpine deposits cover the lowland of the basin. Figure 2 shows a concise geological map and a schematic geological section (AB) of the Glafkos River basin. The post-alpine deposits can be distinguished in the upper and lower relief zones (Zelilidis et al., 1988; Rozos, 1989; Mandilaras et al., 1999). The upper relief zone, at a distance of 2545 km from the coast, includes Neogene and Quaternary sediments, which consist of alternated layers of pebbles and cobbles, sands, marls and clays, as well as consolidated and unconsolidated conglomerates. The lower coastal zone is covered by Quaternary deposits in which a 145 km2 multilayer aquifer is developed in uvial deposits, such as talus formations, terraces, and deltaic deposits, the hydrogeological behavior of which depends on the grain size, the thickness and the stratigraphic spreading. The landward part of the aquifer (upstream of the valley) consists mainly of coarse-grained material (sands and pebbles), whereas ne-grained sediments (clays, clayey silts and marls) prevail in the coastal part. The increasing thickness of the pelitic-clay layers toward the outlet of basin contributes to the development of artesian phenomena in the underlying coarse-grained formations. Thus, the unconned aquifer becomes progressively semi-conned or conned in the downstream zone where multiple layers of ne sediments interfere. The aquifer is mainly recharged by lateral leakage along the riverbed and by the direct inltration from precipitation (Stournaras et al., 1991; Lambrakis et al., 1997). The salinization problems of the coastal aquifers of Glafkos basin are limited in the sediments of the lower coastal area, which lack lithological uniformity both vertically and horizontally. During the period 19752002, the mean annual runoff of the Glafkos River at the entrance in the Quaternary deposits area was measured at 138 m3 s 1 , corresponding to 437 106 m3 of water. According to Mandilaras (2005), similar measurement carried out during the hydrological years 19992002 at the outlet of the river showed that the quantity of the surface water reaching the sea was about 0423 m3 s 1 , or 1335 106 m3 year 1 . For the same years, the direct abstractions from the river water for domestic and agricultural purposes are estimated as 13 106 m3 year 1 ; thus, the inltration water through the riverbed to the aquifer was 17 106 m3 year 1 . Lambrakis et al. (1997) estimated a value of 13 106 m3 year 1 for the same parameter. The precipitation reaching the Quaternary deposits was 07 m, or
Hydrol. Process. 22, 611622 (2008) DOI: 10.1002/hyp

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Figure 2. Concise geological map and schematic geological section of Glafkos River basin (Lambrakis et al., 1997; modifed by Voudouris et al. (2004))

104 106 m3 year 1 (Mandilaras, 2005). The real evapotranspiration, calculated by the ThornthwaiteMather method, reached 713% of the precipitation and is 05 m, or 74 106 m3 year 1 . If runoff is considered to be negligible on the almost at area of the Quaternary deposits, then the precipitation water that inltrates to the aquifer is estimated as 3 106 m3 year 1 . Additionally, the quantity of groundwater reaching the same aquifer from lateral recharge from the adjacent carbonate formations is calculated to be 66 106 m3 year 1 . During the years 19992002, the groundwater abstractions throughout the pumping well of the area were calculated as 18 106 m3 year 1 ; the aquifer discharge to the sea was estimated as 2 106 m3 year 1 (Mandilaras, 2005). Based on the parameters presented above, there is a groundwater surplus of 6 106 m3 year 1 . From measurements during the years 19992002, the difference between dry and humid periods at groundwater level, was 6 m year 1 and the mean value of the aquifer specic storage was 006. From the above values, and given the extent of the aquifer (1456 km2 ), it can be concluded that the groundwater live storage is about 5 106 m3 year 1 and is quite similar to the estimation value of the groundwater surplus.

MATERIAL AND METHODS Water samples for chemical analysis were obtained from 45 representative wells in the alluvial aquifer and three
Copyright 2007 John Wiley & Sons, Ltd.

surface-water sampling points. Tables I and II present the results of chemical analyses of the periods March 1999 and February 2002. Physicochemical parameters such as temperature, pH, electrical conductivity and alkalinity were measured in situ. For the determination of Cl , SO2 4 , NO3 , NO2 , C , NH , Br and I , water samples were analysed on PO3 4 4 the day following their collection. Water samples for the determination of Ca2C , Mg2C , NaC , KC , were rst ltered through 045 m lters and then analytical-grade acid was added to the samples until pH 2 was reached. The chemical analyses were carried out in the Hydrogeology Laboratory of the University of Patras. The cations (Ca2C , Mg2C , NaC and KC ) were measured using the atomic absorption spectrometry technique. For the anions 3 C determinations, the SO2 4 , NO3 , NO2 , PO4 and NH4 contents were determined using the spectrophotometer technique, Cl content was obtained by titration using AgNO3 , and suitable ion-selective electrodes were used for the determination of Br and I contents. The quantitative determination of Br , in selected water samples, was conrmed with the ion chromatography method. The reliability of chemical analyses was checked using the mass balance and electroneutrality equations and their analytical error did not exceed 3%. Hydrochemical simulations were made using the PHREEQC software, and the areal distributions of different parameters were obtained by applying the kriging method (Matheron, 1971; Olea, 1974).
Hydrol. Process. 22, 611 622 (2008) DOI: 10.1002/hyp

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Table I. Groundwater chemical composition of alluvial aquifer of Glafkos River basin for the sampling period of March 1999a
1

pH
1 1

Copyright 2007 John Wiley & Sons, Ltd. SO2 NO3 NO2 Ca2C Mg2C 4 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) NaC (mg l 1 ) I ) (mg l ) 02056 00379 00838 00087 00220 00509 00087 00110 00100 00100 00087 00160 00130 00130 00092 00092 00092 00110 00080 00034 09555 177 183 219 260 205 212 272 323 313 348 310 353 323 500 240 323 662 260 323 376 180 317 74710 15700 27000 1494 7620 8740 1265 2687 985 1765 1971 1168 1420 920 2101 570 1494 1595 1690 570 11575 668 665 420 960 060 260 313 210 129 035 120 120 040 090 117 050 039 082 105 020 060 513 275 0310 1340 0320 2040 0050 0160 0100 0880 0025 0160 0049 0 0290 0150 0150 0061 00 1092 651 145 301 010 049 209 010 009 008 015 028 009 009 018 009 009 018 017 009 005 8840 020 KC NH3 Br (mg l 1 ) (mg l 1 ) (mg l 1900 1370 1950 190 1160 216 210 270 170 115 322 62 62 120 360 106 200 850 70 240 3290 150 3100 2380 1890 2070 10210 4960 1628 1580 1410 124 682 31 308 310 2950 310 2550 836 1980 484 00 719 0010 0003 0010 0003 0023 0003 0010 1920 0007 0053 0007 0109 0003 0017 0003 0020 0 0 0110 32710 17920 18000 9760 20760 24850 9680 9520 7400 7600 11400 7520 5600 6410 8080 5130 9680 15200 8800 5960 4450 1550 7390 816 4440 576 1704 2430 1104 240 1010 288 408 120 720 1700 768 1750 480 720 192 456 1500 058 103 rBr / 104 rI / rCl rCl 0351 0303 0384 143 0580 0326 149 248 246 146 0607 394 293 227 154 207 213 106 180 215 0123 rSO4 / rCl rNa/ rCl 00860 02895 02364 08266 08094 00366 09528 16104 10933 05316 03451 03698 03698 05547 16136 06322 12430 21677 04142 28629 011 09730 0705 0692 0683 1355 1109 0309 1197 3342 1321 1928 0514 1567 2139 0887 1964 0709 1936 0848 2085 1418 082 0904

Water sample point

T ( C)

Cond. (S cm 1 )

HCO3 Cl (mg l 1 ) (mg l

D. MANDILARAS, N. LAMBRAKIS AND G. STAMATIS

(1) (10) (11) (19) (20) (24) (25) (26) (27) (28) (30) (32) (34) (35) (37) (40) (75) (85) (88) River Seawater Rain

711 736 730 733 696 685 739 717 760 705 706 712 717 707 744 724 741 701 746 787 811 719

152 161 160 160 170 166 164 172 153 146 192 149

5510 2230 3700 574 1567 1882 618 325 390 499 946 463 390 490 649 379 640 874 585 308 49800 208

2758 2928 2904 2867 4380 2904 3026 2928 2379 2746 2807 2685 2807 2550 2416 2160 2843 3758 2623 1830 1500 291

16340 3500 6100 170 1060 4360 163 124 115 190 400 114 124 160 165 124 119 290 125 6 2 21700 114

Hydrol. Process. 22, 611622 (2008) DOI: 10.1002/hyp

a In

ion ratios r denotes meq l

Table II. Groundwater chemical composition of alluvial aquifer of Glafkos River basin for the sampling period of February 2002
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Copyright 2007 John Wiley & Sons, Ltd.

Water sample point 7100 390 142 1570 5620 11800 323 103 231 2620 138 4 1 126 9 9 123 7 9 6 5 170 9 5 7 3 5 4 1150 380 280 600 1380 2200 290 260 450 310 210 180 130 230 2 0 3 0 2 0 190 390 210 320 1936 3432 2948 2904 2288 1892 484 2288 2684 2860 1672 1892 1760 2904 792 704 748 1276 3212 440 2552 0026 0020 0007 0026 0003 0007 0003 0017 0053 0020 0023 0010 0010 0013 1525 0003 0020 0 0023 0 0007 006 006 008 011 011 1225 009 055 068 007 006 004 013 007 009 009 004 004 009 006 006 17212 10006 9087 13251 13772 20226 9053 9799 12755 17045 9736 7469 7764 8824 5232 6802 7481 8430 11140 5969 10680 3371 1172 886 2033 3148 7929 793 810 1022 1548 760 764 816 820 881 636 680 707 1003 844 1272 35635 4005 2106 8729 32934 66549 2390 1141 2265 7823 1213 844 1251 1009 3598 1506 1579 1072 1645 588 1146 948 380 244 411 834 1856 251 183 251 445 202 167 193 167 321 174 170 189 186 158 209 0524 0 0 0341 0195 1865 0 0 0024 1402 0012 0 0012 0 2535 0 0024 0012 0 0195 0012

pH

Eh HCO3 Cl SO2 NO3 NO2 PO3 Ca2C Mg2C NaC KC NH3 Br T Cond. 4 4 ( C) (S cm 1 ) (mV) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) 190 033 020 060 145 290 026 016 027 089 012 009 010 009 014 006 007 014 014 007 016

103 rBr / rCl 118 378 618 169 114 109 357 697 522 150 376 992 349 417 501 348 465 368 653 431 128

rSO4 / rCl 01198 07206 14583 02826 01816 01379 06640 18669 14407 00875 11255 32470 07631 17182 01203 02809 02276 08266 30362 21276 43827

rNa/ rCl 0774 1584 2287 0857 0904 0870 1141 1708 1512 0460 1355 3174 1531 1572 4511 2940 3746 0972 2670 1242 3273

(1) (4) (8) (10) (11) (13) (16) (18) (20) (24) (26) (27) (29) (30) (31) (32) (34) (35) (37) (40) (42)

722 718 749 703 738 717 718 722 712 724 714 752 751 742 745 740 748 739 725 775 711

160 172 167 174 169 169 175 179 182 168 161 152 172 167 176 162 168 150 172 159 173

2840 802 673 1350 2410 4680 665 651 859 1590 640 252 569 664 578 490 419 572 748 432 708

227 198 233 186 238 128 88 234 110 180 124 138 20 130 79 133 192 238 124 164 133

2684 3233 2867 3477 2574 3599 2891 3050 3684 3037 2976 2440 2501 2562 2671 2525 2806 2635 3257 2000 3440

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615

616

Table II. (Continued ) 103 rBr / rCl 009 017 111 018 012 052 023 037 019 011 025 023 020 014 007 036 025 012 012 038 004 470 963 139 411 763 186 957 222 450 464 564 575 290 375 331 319 549 458 655 363 315 rSO4 / rCl 17609 73958 01048 19927 39583 03247 71885 02938 24125 21914 43237 16482 00033 21914 06294 06656 21184 06836 23450 05466 19086 rNa/ rCl
D. MANDILARAS, N. LAMBRAKIS AND G. STAMATIS

Copyright 2007 John Wiley & Sons, Ltd.

Water sample point 8 4 8 0 3530 193 7 1 1230 107 730 187 108 195 175 304 162 9 4 500 199 119 8 2 460 6 2 200 800 500 520 380 540 1040 290 610 320 1140 390 0 480 8 0 450 570 110 260 340 160 2156 2376 1936 924 3124 2244 1276 3168 660 2948 4048 2816 352 3608 1804 3344 3652 1188 1540 1848 704 0007 0010 0017 0003 0023 0020 0003 0017 0007 0020 0020 0725 0013 0003 0010 0036 0013 0003 0003 0023 0030 004 010 007 024 007 006 011 012 008 009 020 010 007 005 004 006 009 016 007 005 004 8411 10832 17884 11538 11171 8992 12680 10688 10435 9086 15535 11484 7621 9603 7422 13605 14238 7111 8837 9756 5613 1123 1151 1884 987 894 1566 1295 942 941 780 1140 987 708 729 754 1582 1071 915 726 879 440 807 2108 12295 2123 1009 10813 2103 4377 1763 866 2299 2523 1929 1116 762 3673 1834 2391 974 3609 446 180 285 463 272 205 440 247 288 302 214 570 299 230 221 166 295 290 445 193 313 143 0 0037 1109 0 0 0 0061 0 0 0 0658 0240 0744 0 0012 0317 0195 0 0 0024 0012

pH

Eh HCO3 Cl SO2 NO3 NO2 PO3 Ca2C Mg2C NaC KC NH3 Br T Cond. 4 4 ( C) (S cm 1 ) (mV) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 ) (mg l 1 )

(45) (57) (67) (72) (75) (78) (85) (100) (105) (107) (112) (119) (120) (127) (129) (131) (135) (137) (140) (151) River

718 716 708 719 761 733 721 720 740 738 695 711 735 724 758 679 676 726 745 714 796

176 186 154 193 176 170 179 168 189 173 186 174 173 163 158 178 190 185 178 164 137

302 910 1730 772 729 1220 861 928 725 677 1020 930 557 747 515 1060 920 575 628 804 382

175 174 203 260 185 196 70 156 65 173 120 122 149 184 176 211 176 68 238 226 114

2745 3172 2598 3599 3233 3318 3538 2989 2989 2562 3745 3660 2684 2391 2403 4087 3965 2867 2806 3050 1684

1482 4063 0537 1696 2192 1356 3031 0925 1454 1237 1818 2223 0979 1062 1250 1133 1421 3098 1832 1210 1109

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RESULTS Groundwater quality and hydrochemical processes During the last decade, a rapid improvement of the groundwater quality of the alluvial aquifer of Glafkos River basin has beenobserved. This is due to the decrease of groundwater abstraction, which has resulted from a reduction in water consumption compared with the resent past (Mandilaras and Voudouris, 2001). The improvement of the groundwater quality is also related to the fact that great amounts of brackish groundwater from the lower coastal part reach the sea through wells with freely owing water. Especially for the investigation period 19992002, a decline of the groundwater electrical conductivity of 1200 S cm 1 was recorded. However, high values of groundwater salt concentration are present in a lower coastal zone of 10001200 m width. As an example, the maximum Cl and NaC concentration was 1634 mg l 1 and 747 mg l 1 respectively. The electrical conductivity in this lower coastal zone amounts to 5510 S cm 1 and the NaCaCl groundwater type dominates. In the upper part of the alluvial aquifer of Glafkos basin, far away from the coast, the Cl concentration varies between 7 and 15 mg l 1 , whereas the concentration of NaC ranges from 8 to 15 mg l 1 . In this area, the electrical conductivity values range from 400 to 700 S cm 1 and the CaHCO3 groundwater type dominates. Occurrence of salinization could be indicated by the 25 mg l 1 Cl concentration curve, taking into consideration that the mean Cl concentration was 167 mg l 1 for rainwater and 77 mg l 1 for surface water of the Glafkos River. In Figure 3, which presents the distribution of Cl concentration during the study period, the groundwater quality improvement can also be observed. Figure 4a shows the piezometric map of the Quaternary deposits aquifer for the period of March 2002. The groundwater ow path is in a southeast to northwest direction following the Glafkos river direction in the middle section of the area. Figure 4bd shows the distribution of Cl , NaC and CaC concentrations along this

groundwater ow path. The Cl concentration decreases landward, following a hyperbolic curve. Since the Cl ions are considered as chemical inert, the increase of Cl concentration along a ow line could be attributed to seawater intrusion and mixing with the fresh water of the aquifer. A decrease of Cl concentration as a result of the aquifer remediation is also clearly observed during the 1999 to 2002 sampling periods. The sodium concentration varies in a similar way. The Ca2C concentrations shown in Figure 4d decrease signicantly from the coast to the inland, but increase at a distance of 10001200 m from the coast, showing a change that could be attributed to ion-exchange phenomena. Ion-exchange phenomena are conrmed from the results illustrated in Figure 5, where the solid line represents the concentration/dilution characteristic for seawater. It is observed that Ca2C and NaC ions exceed those of Cl . The high Ca2C concentration is attributed to the ion-exchange processes during the seawater intrusion according to the equation NaC C 1/2CaX2 $ NaX C 1/2Ca2C where X is the exchanger. The rNaC /rCl ratio is 086 10% in marine water (Mandel and Shiftan, 1981; Appelo and Postma, 1994). During March 1999, in many samples of the coastal part of the study area, the rNaC /rCl ratio ranged between 031 and 071, indicating NaC decit and Cl excess. This decit suggests that seawater intrusion in this place could still be active. In most samples of February 2002 the values of rNaC /rCl ratio were higher than 0782 (Table II). This indicates that, during this period, NaC was in excess not only in the lower coastal part of the aquifer but also in the upper part. That could be attributed to a refreshening (remediation) process; Ca2C ions, due to the aquifer recharge with fresh water, displace NaC ions on the exchange sites of the aquifer sediments. In Figure 6a, signicant excess of SO2 4 ions toward Cl ions is shown for most samples of the study area. Figure 6b demonstrates two distinct tendencies concerning the relation of HCO3 with Cl and SO2 4 .

Figure 3. Cl distribution map (concentration in mg l Copyright 2007 John Wiley & Sons, Ltd.

) for the sampling periods (a) March 1999 and (b) February 2002

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Figure 4. Piezometric map of Quaternary deposits (February 2002): (a) groundwater ow path follows southeast to northwest direction; distribution of (b) Cl , (c) NaC and (d) Ca2C concentrations along the ow-path lines

Figure 5. Scatter plot diagrams showing the relationships among Cl , NaC and Ca2C for the period of February 2002. The solid line represents the concentration/dilution characteristic for seawater

Thus, the HCO3 ions, which characterize the fresh water of the area, are linearly correlated with the Cl ions, which characterize marine water. This could be attributed to mixing of fresh and marine waters. The HCO3 ions are also linearly correlated with the SO2 ions, 4 which characterize gypsum waters. Although gypsum formations are not known in the broader area, they could exist in the Neogene formations underlying the alluvial deposits. As Figure 7 shows, most of the samples are saturated in calcite, are almost saturated in dolomite, and all samples are undersaturated in gypsum. This gure presents a classic case of the dilution of dolomite (dedolomitization) taking place in the presence of calcite and gypsum,
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like the one described by Plummer et al. (1990). According to those authors, in an aquifer containing dolomite and calcite, one might expect that groundwater is close to equilibrium for both minerals. If gypsum also exists, then the increasing calcium concentration due to the dissolution of this mineral causes calcite precipitation. The carbonate concentration decreases as calcite precipitates, and this provokes the dissolution of dolomite. Thus, the process that could be at the origin of the linear relation between HCO3 and SO2 4 is correctly the incongruent dissolution of dolomite driven by gypsum dissolution. In general, the samples of the alluvial aquifer presented a decrease of the ratios rSO2 and rNaC /rCl 4 /rCl along the groundwater ow direction, from the upper zone towards the coastal part of the alluvial aquifer. These ratios are similar and in some cases less than the respective ratios of seawater. Determination of the salinization zone The diagram of Br versus Cl (Figure 8) with high linear correlation coefcient (r D 099) exhibits a common origin of Cl and Br for the sampling period of March 1999. The observed variations could be attributed to the contribution of ions from the rock minerals and the dilution of chlorides into the aquifer (Morell et al., 1986). It is known, that the Br concentration is lower than 01 mg l 1 in fresh water and lower than 1 mg l 1 in coastal areas, whereas it reaches 68 mg l 1 in seawater
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Figure 6. (a) Scatter plot diagram of the Cl

versus SO2 4

ions and (b) ternary diagram of Cl , SO2 4 February 2002

and HCO3 ions for the sampling period of

Figure 7. Calcite, dolomite and gypsum saturation indices as a function of dissolved SO2 4 content

Figure 8. Scatter plot diagram of Br versus Cl for the sampling period of February 2002

(Rankama and Sahama, 1950). The presence of I ions, associated mainly with seawater, indicates seawater intrusion (Lambrakis, 1991). The I concentration is generally lower than 001 mg l 1 in fresh water and lower than 01 mg l 1 in coastal areas, whereas in seawater it exceeds 1 mg l 1 . The Br concentration varies from 008 mg l 1 to 651 mg l 1 in the groundwater of the study area, whereas that of I ranges from 0003 to 02 mg l 1 . Generally, in those parts of the study area where seawater intrusion does not occur, the Br and I concentrations are lower than 02 mg l 1 and 002 mg l 1 respectively. The scatter plot diagram of rBr in relation to rBr /rCl suggests that the groundwater samples from
Copyright 2007 John Wiley & Sons, Ltd.

the coastal zone are different from the others, which form a characteristic group. In particular, groundwater samples show an rBr /rCl decrease along the groundwater ow path from the upper relief zone toward the coastal zone. Owing to seawater intrusion, the rBr /rCl values are identical to that of seawater (Figure 9a). Variation from this behaviour could occur as in case of seawater evaporation, where the remaining phase is progressively enriched in Br in relation to Cl , allowing an increase of the rBr /rCl ratio (Sanders, 1991; Edmunds, 1996). The use of pesticides could also cause an increase of Br concentration in groundwater (Flury and Papritz, 1993; Davis et al., 1998), resulting in an rBr /rCl increase in groundwater. As is shown in Figure 9b, the rNaC /rCl ratio presents a similar behaviour, decreasing along the groundwater ow path from the upper zone toward the coastal zone, where it is identical to or less than that of seawater. According to the spatial distribution of Br in groundwater, it is ascertained that during the sampling period of March 1999 (Figure 10a) the concentration of this ion was generally lower than 02 mg l 1 in the upper zone of the study area. A gradual but signicant increase of Br concentration, with values ranging from 07 to 65 mg l 1 , was observed in groundwater of that part of the coastal aquifer located 12 km from the coastline. Figure 10b indicates that the high Br concentration, ranging from 02 to 29 mg l 1 , for the sampling period of February 2002 is restricted in a zone not wider than 500 m from the coastline. The presence of seawater intrusion was also indicated by the rI /rCl ratio in groundwater of coastal aquifers
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620

D. MANDILARAS, N. LAMBRAKIS AND G. STAMATIS

Figure 9. Scatter plot diagram of Br versus the ratios (a) rBr /rCl and (b) rNaC /rCl for the sampling period of February 2002

Figure 10. Distribution of bromide concentration (mg l

) in groundwater for the sampling periods of (a) March 1999 and (b) February 2002 (Mandilaras, 2005)

(Lambrakis, 1991). Figure 11a and b presents the distribution maps of the rBr /rCl ratio and rI /rCl in groundwater for the sampling period of March 1999. As shown in Figure 11a, values of rBr /rCl lower than 25 10 3 appear in the coastal zone, with minimum values near the coastline (rBr /rCl < 15 10 3 ). In those parts of the study area where seawater intrusion

takes place, the rBr /rCl ratio shows similar values to that of seawater (18 10 3 ). Similar estimations are given by Alcala and Custodio (2004) for Spanish coastal aquifers, where the rBr /rCl ratio shows values comparable to those obtained from seawater (152 10 3 ), as well as by Andreasen and Fleck (1997) for Chesapeake Bay, USA (166 10 3 204 10 3 ).

Figure 11. Distributions of (a) rBr /rCl and (b) rI /rCl ratios in groundwater for the sampling period of March 1999 (Mandilaras, 2005) Copyright 2007 John Wiley & Sons, Ltd.

Hydrol. Process. 22, 611622 (2008) DOI: 10.1002/hyp

SALINIZATION MAPPING OF THE GLAFKOS RIVER BASIN AQUIFER

621

In the aquifers of the upper zone, a gradual but signicant increase of the rBr /rCl ratio was observed, reaching 66 10 3 99 10 3 (Tables I and II). The rBr /rCl ratio in surface waters of the Glafkos River, which are the main recharge source of the aquifers, ranged from 25 10 3 to 68 10 3 (Tables I and II). During the 3-year period of this study (19992002), the extent of the aquifer zone characterized by a low value of rBr /rCl ratio was considerably reduced from 1100 m to about 800 m from the coast. The distribution map of rI /rCl (Figure 11b) shows that values lower than 7 10 5 are observed in the coastal area, whereas lower values (27 10 5 ) are shown toward the coastline. Generally, in those parts of the study area where seawater intrusion takes place, the rI /rCl ratio has similar values to that of seawater (12 10 5 ). In the aquifers of the upper zone, a gradual but signicant increase of the rI /rCl ratio is observed (39 10 4 ). The mountainous surface waters of the Glafkos River also show similar values, ranging from 16 10 4 to 26 10 4 . These values correspond to groundwater with good recharge conditions, which is supported by the fact that the aquifer recharge source is the Glafkos River. In general, the signicant increase of the I and Br concentrations around the Glafkos River is due to the increased permeability of the alluvial deposits.

the coastline these values become higher. Within the same zone, the values of the rBr /rCl ratio range between 15 10 3 and 25 10 3 , which is similar to seawater values. At greater distances, corresponding to the middle and upper alluvial zones, a gradual but signicant increase of the rBr /rCl ratio up to a value of 99 10 3 occurs. Similar values of the rBr /rCl ratio (25 10 3 68 10 3 ) are observed in the surface water of the Glafkos River, which mainly recharge the alluvial aquifers. During the study period (19992002) the extent of the zone of the aquifer that is characterized by a low rBr /rCl ratio was considerably reduced from about 1100 m to about 800 m from the coast. Similar conclusions can be derived from the study of the rI /rCl ratio distribution values of groundwater. The samples of the period of July 1999 exhibit the lowest values (<7 10 5 ) in the coastal zone. On the contrary, in aquifers of the middle and upper alluvial zones, a gradual but signicant increase of the rI /rCl ratio up to a value of 39 10 4 is observed, which is close to the surface water value of the Glafkos River (16 10 4 26 10 4 ).

ACKNOWLEDGEMENTS

CONCLUSIONS The groundwater quality of the Glafkos alluvial basin has been degraded in a coastal zone of 10001200 m width because of seawater intrusion. A rapid improvement has occurred during recent years, due to the positive water balance and discharges of great water quantities that ow to the sea through wells with freely owing water. Focusing on the coastal zone, a mean decrease of the electrical conductivity of about 1200 S cm 1 occurred in the years 19992002; this reduction corresponds to 200 mg l 1 and 50 mg l 1 for Cl and SO2 ions 4 respectively, whereas for sodium and magnesium the reduction was respectively 100 mg l 1 and 15 mg l 1 . Dilution, mineral deposition and ion-exchange processes mainly control the groundwater chemical composition. Therefore, Ca2C concentrations exhibit a decrease from the coast to the inland at a distance of approximately 1000 m and then an increase that might be attributed to ion-exchange processes. Ion balances based on the NaC , Cl and Ca2C concentrations using hydrochemical diagrams conrm these processes. Groundwater samples show a decrease in the values of the rSO2 and rNaC /rCl ratios along the 4 /rCl groundwater ow path, from the upper zone to the coastal zone, where they reach the ratio values of seawater. Spatial distributions of the Br and I ions reveal that their concentrations are lower than 02 mg l 1 and 002 mg l 1 respectively in the greater part of the aquifer, whereas in the coastal zone of 112 km width from
Copyright 2007 John Wiley & Sons, Ltd.

We wish to express our gratitude to the Editor and the referees for their careful readings of the rst version of this manuscript. Their comments, suggestions, and remarks proved indispensable in helping us improve the style and presentation of this paper.

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Hydrol. Process. 22, 611622 (2008) DOI: 10.1002/hyp