Journal of Hydrology 323 (2006) 230243 www.elsevier.

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Multicomponent heterovalent chromatography in aquifers. Modelling salinization and freshening phenomena in eld conditions
Nikolaos Lambrakis*
Department of Geology, Section of Applied Geology and Geophysics, University of Patras, 26500 Patras, Greece Received 16 December 2004; revised 31 August 2005; accepted 2 September 2005

Abstract Analysis of hydrochemical data using diagrams and the geochemical transport model PHREEQC conrmed that for the Argos plain aquifer and for other heterogeneous conned alluvial coastal aquifers in Greece, the variation of water qualities along a ow path has basically a chromatographic origin due to seawater intrusion and freshening processes. Additionally, calcite precipitation, dolomite and gypsum dissolution take place. Intense fertilization and overexploitation of the area resulted in degradation of the groundwater quality by high amounts of nitrate ions and increased salinization. The main physical factor affecting groundwater quality in this area is the cation exchange capacity that is calculated to be 4.3 meq(100 gr)K1. Good adaptation of the transport model to the eld data showed that the model can be used to predict the freshening process after an articial recharge. Hence in a rst stage for ClK, there is a continuous decrease to the initial fresh water concentrations corresponding to about 11.5 pores volumes that should have been shifted through the aquifer, while for both cations Ca2C and Mg2C this decrease is even lower and leads to concentrations lower than that of the initial fresh water. Complete restoration of the aquifer requires a great amount of recharge water that should be transported through the aquifer and corresponds to 32 pores volumes. q 2005 Elsevier B.V. All rights reserved.
Keywords: Argos; Alluvial aquifer; Hydrogeology; Hydrochemistry; PHREEQC

1. Introduction The Valocchi et al. (1981a,b) experiment has clearly shown chromatography patterns developed during injection of fresh water in a brackish water aquifer namely direct exchange Ca/Na or freshening

* Corresponding author. Tel./fax: C30 610 997782. E-mail address: nlambrakis@upatras.gr

process. The process is due to the presence of exchangers that may consist of clay minerals, organic matter, and oxides and hydroxide content so that the variation of the ground water cation concentration depended mainly on cation exchange capacity of the aquifer. In the opposite case the inverse exchange, Na/ Ca takes place when brackish water reach zones of the aquifers previously occupied by fresh water (Foster, 1950; Back, 1966; Lawrence et al., 1976), and that occurs very often in nature especially when the coastal

0022-1694/$ - see front matter q 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.jhydrol.2005.09.002

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aquifers are overexploited and seawater intrusion occurs (Fidelibus et al., 1993; Pulido-Laboeuf, 2004). The behavior of the chemical species depends on several factors such as differences between the selectivity coefcients, value of the CEC, contrast between the chemical composition of the injected uid and the uid initially resident in the pores of the sediment and dispersion. Many researchers have studied such situations (Appelo and Willemsen, 1987; Beekman and Appelo, 1990; Appelo and Postma, 1993) through laboratory simulations based on the principle of the ionic chromatography. Others described similar characteristics at the eld conditions (Edmunds and Walton, 1983; Chapelle and Knobel, 1983). Many coastal aquifers in Greece are subjected to intensive exploitation. The augmented needs in water of the last two decades in Greece and the prolonged dry period of the nineties in combinations with the lack of any management strategy of groundwater resources caused by a serious decline of the groundwater table (Mimikou et al., 1991; Lambrakis and Daskalaki, 1999). This decline that in many cases of coastal porous aquifers reached the 50 m (Petalas and Diamantis, 1999), produce seawater encroachment and the development of exchange phenomena. The quaternary deposits of Argos plain extend for at least 200 km2 and a have mean thickness of 100 m. The groundwater quality of these deposits has deteriorated due to intensive exploitation of the aquifers and seawater encroachment. Intensive groundwater pumping in Argos plain started in the 1950s and initially led to salinization of the shallow coastal aquifer layers. Due to increased demands for irrigation water, both well number and depth increased and salinization affected even the deepest aquifers. The number of boreholes is presently estimated to be more than 15,000. At the same time, intense application of nitrate fertilizers has caused deterioration of groundwater quality. Due to the importance of the Argos plain aquifers, in the earl 1960s the Ministry of Agriculture together with expert foreign organizations (FAO and TAHAL) designed a program in order to rationally manage the groundwater and prevent seawater encroachment. The rst articial recharge experiment that took place in the Argos area concentrated on a small number of wells for a time period of 270 days during 19651967

and the results were very satisfactory (Thanos, 1994). Since then, extensive exploitation of the aquifers has continued resulting in further sea water intrusion and in the 1990s a larger articial recharge was employed. It is estimated that, from 1990 to 1998, more than 20! 106 m 3 of fresh watercorresponding to 166 mm of effective precipitationreached the aquifers (Giannoulopoulos, 2000). The aim of this article is to investigate multicomponent heterovalent chromatography due to seawater intrusion and also to articial recharge in Greek coastal areas, and nd out how this process affects groundwater chemical composition. One major question that the article attempts to answer relates to changes in groundwater quality during refreshening process, with the amount of recharge water injected into the aquifers. This research focused on the continuity of a series of studies with similar intention that was the research of mechanisms that contribute to the formation of the groundwater chemical characteristics of the coastal aquifers due to seawater intrusion. Many coastal aquifers in Greece have been investigated for this purpose from the author during the last 10 years and the results of the research has been reported to previous articles (Lambrakis, 1997; Lambrakis et al., 1997a,b; Kallergis et al., 1997; Lambrakis and Daskalaki, 1999; Lambrakis and Kallergis, 2000; Lambrakis et al., 2001). Among these aquifers, the coastal plain of Argos constitutes the most suitable example because of its geological conditions. It is a typical coastal area that suffers from agricultural activities with serious impact on groundwater quality. In addition, its hydrogeological conditions are relatively known from previous investigations (Poulovassilis et al., 1996; Giannoulopoulos, 2000; Lambrakis et al., 2001).

2. Theoretical approach 2.1. Ion exchange and chromatography Sediments in general have a natural ion exchange capacity. Additionally, for different cations, the selectivity of sediments, namely the matrix of an aquifer or exchanger, varies so that transport velocity of the cations within the groundwater is seriously

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affected from it. When studied in the laboratory experimental column, retardation of the transport of these cations induces their separation, and this phenomenon is known as chromatography. It has been known since the 1950s that NaHCO3 waters in coastal areas are connected with cation exchange (Foster, 1950; Back, 1966). Similarly, CaCl2 waters are also connected with cation exchange (Lloyd and Heathcote, 1985). NaHCO3 waters indicate the occurrence of the freshening process, when Ca2C of the recharge water is replaced by the NaC of the matrix of an aquifer previously contaminated by seawater intrusion. During this process, Ca2C from the aquifer matrix replaces NaC of the NaCl saline water (Appelo and Postma, 1993). Generally, when equilibrium exists among solute and exchangeable cations, the following law of mass action can be applied to this exchange (Appelo, 1997): 1=zi izi C 1=zj j KXzj 4 1=zi i KXzi C 1=zj jzj with,
=zi zjC 1=zi =bj j iziC 1=zi Ki=j Z b1 i j 1=z

qiZbi.CEC.10rbqK1, where bi(%), the equivalent fraction of an exchangeable cation, CEC [meq(100 gr)K1 dry sample] is the cation exchange capacity, r b (g cmK3 ) the bulk density of the sediments, and q (%) is the water lled porosity.

3. Description of the eld example 3.1. Geology of Argos plain The pre-Alpidic metamorphic background of the Argos plain consists of sericitisated mica-schist and phyllite graphites, folded with quartzites with thick grey limestone dominating its upper strata. The Argos plain is composed mainly of rocks of the Alpine system (Fig. 1). The isopic zone of Tripolis is the deepest, followed by the isopic zones of Olonos Pindos and Subpelagonian. These two isopic zones overthrust each other onto the previously mentioned zone (Tripolis zone). Alpidic formations cover the mountainous areas of the plain and are composed of calcareous rocks and ysh. They are of Mesozoic age and consist of thin to thick-bedded limestones and dolomites. Chert is abundant at the base of the OlonosPindos unit. The whole Alpine system is many hundred metres thick and has been affected by tectonic stress and karst phenomena. At the edge of Argos plain, major coastal karstic springs rise through the carbonate rocks of the OlonosPindos zone. In the northern parts of the plain, hilly areas are covered by Neogene sediments of marls, sandstones and conglomerates at altitudes over 100 m, while the lowland is covered by Quaternary deposits (Jacobshagen, 1986; Papastamatiou et al., 1970; Tataris et al., 1970; Jacobshagen et al., 1978). The Quaternary deposits have thicknesses varying from some metres at the border to over 200 m in the middle of the plain. They consist mainly of movable clay and clastic (sands, gravels, conglomerates) sediments (Zervas, 1965). The different sedimentation phases of Argos plain are marked by the presence of chemical, organic and bioclastic sediments that have limited distribution. Faults of a NWSE and SWNE direction dominate the graben of Argos.

(1)

(2)

with bi;j Z i; j KX the equivalent fraction and X b Z1 (3) Eqs. (1)(3) allow the determination of all bs in a multicomponent solution when the aqueous concentration is known. 2.2. Solute transport In the case of one-dimensional ow, as in an experimental column, changes in the chemical composition of groundwater due to advection, dispersion and sorption (reactions) processes, can be expressed by the following equation:        2  vC vC vC vq Z DL Kv K (4) vt x vx t vt vx2 t where C is the concentration of the chemical substance in moles/L, t is time (s), x is distance (metres), DL is the coefcient of longitudinal hydrodynamic dispersion (m2 sK1), v is the ow velocity (m sK1), and q is the concentration of solid, expressed as pore water concentration (moles LK1). In the case of ion exchange

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Fig. 1. Geological structure of the study area modied from Papastamatiou et al. (1970); Tataris et al. (1970); Jacobshagen (1986). (1) Quaternary deposits; (2) Neogene deposits; (3) Carbonates of Pelagonian units; (4) Flysch of Pindos units; (5) Carbonates of Pindos units; (6) Flysch of Tripolis units; (7) Carbonates of Tripolis units; (8) Schists-Phyllites of Arnas units; (9) Fault, visible or probable; (10) Overthrustupthrust; (11) Geological section. (Lambrakis et al., 2001).

3.2. Hydrogeology of Argos plain Following the Kopen classication, the Argos region belongs to the Csa climatic type. The climate is mild with a dry summer period and the mean temperature of the warmest month is over 22 8C. The lowland receives a mean annual precipitation of 500, 350 mm of which feed the real evapotranspiration

(Etr) process while the other 150 mm mainly recharge the aquifers since runoff is practically insignicant (Poulovassilis et al., 1993). In the wider catchment area the above parameters vary. The mean annual precipitation rises to 700 mm while Etr is estimated to be approximately 580 mm. The most important aquifers in the broader area have developed in carbonate rocks. They discharge

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mainly into the coastal karstic spring and partially, through lateral seepage, into the alluvial aquifers of Argos. In the alluvial formations, alternating aquifer beds are present. These conned aquifer beds, which are 57 km in length at the central and coastal parts of the plain, unite at the peripheries of the plain where they form an unconned aquifer the thickness of which decreases at the edge where it terminates. The alluvial materials (cones of debris, ood and river sediments) are not of the same origin and are related with the River Inachos that was displaced from east to west during the Quaternary period (Sabatakakis et al., 1995). The total thickness of the aquifer beds varies between 50 and 60 m with a mean thickness of 56 m. Recharge of the aquifer occurs directly from precipitation, mainly, through riverbeds in the unconned part as well as indirectly, laterally from the carbonate formation and Neogene conglomerates in the periphery of the plain in the areas of Borsa, Fichti and Koutsopodion (Tavitian et al., 1994). Hydraulic parameters calculated from pumping tests and for the total thickness of the alluvial aquifers vary as described in the following (Poulovassilis et al., 1996): Hydraulic transmissivity (T) varies between 300 and 700 m2dK1. These habitual values are low due to presence of ne material in the aquifer beds. However, in some areas values of up to 7260 m2 dK1 are encountered. The storage coefcient varies between 1.7!10K5 and 2.8!10K2. The value derived from pumping tests in the conned part of the aquifer for the purpose of this study was found equal to 5.5!10K3. This is consistent with the mean of the above-mentioned values. Porosity varies between 0.20 and 0.26. As mentioned previously, exploitation of Argos plain groundwater started in the 1950s. The number of deep wells increased through time and natural recharge of the aquifers attempted to balance the groundwater extraction. Using data from the 1960s and then, Poulovassilis et al. (1996), conclude that the groundwater level of Argos plain started to be disturbed after 1969. The same authors estimate that balanced conditions in the aquifer were conserved until 1963. In 1969 the piezometric gure showed positive water levels but, since then a continuous decline of the hydraulic head is observed. In the autumn of 1990, negative absolute piezometric values extended from the coast, to the inland where they

reached 30 m. In spring 1995, the piezometric values observed were the same as those in 1990. From ClK distribution maps of 1965 (Giannoulopoulos, 2000), it is clear that increased salinization of the coastal area begun at that time. In 1975, the isochloride curve of 250 mg LK1 was at mean distance from the sea of about 3.5 km, indicating a mean progress of the saline front of the order of 0.95 m dK1 that took place between the years1965 and 1975. In 1995, the iso-chloride curve of 250 mg LK1 was at a mean distance from the sea of about 6 km, so the progress of the saline front between 1975 and 1995 was 0.82 m dK1. This decrease in saline front progress could be attributed to the regularization of the pumping and to the articial recharge that was applied in a large scale between 1990 and 1998. Between 1963 and 1995, the mean progress of the saline front estimated as above was about 0.5 m dK1.

4. Materials and methods The sampling of groundwater took place during the autumn period of 2000, in a network of 40 monitoring wells uniformly distributed throughout the study area. In order for the samples be representative, the sampled wells were chosen to have more or less the same depth of between 80 and 100 m. A standard screen covered 30% of the tubing and is located at the bottom of the wells. The amount of pumped water varies between 80 and 120 m3 hK1. Physicochemical parameters as pH, EC were measured in situ by using the portable equipment Hanna/HI-8414 and WTW/LF-330, respectively. Alkalinity was also determined in situ by the titration technique. The samples were collected at the well-pump outow and were stored in two polyethylene bottles. The rst sample of 0.5 L volume was ltered and acidied for cation analysis with atomic adsorption, GBC Companymodel 908AA. The anions content, excluding ClK, were determined by using a spectrophotometer of the HACK Company, the model DR/4000. For the determination of ClK content titration techniques were applied by using AgNO3 0.1 N. The chemical analyses were carried out in the laboratory and their analytical error does not exceed 5%, as we can conclude from the evaluation of the results with the use of a suitable software (Lambrakis, 1991).

Table 1 Chemical analyses of groundwater samples from Argos plain (Autumn 2000) and saturation indices
SID ph Eh (mv) 139 242 208 200 K30 228 210 214 213 248 258 218 255 262 238 270 245 235 241 239 200 220 214 250 239 245 239 250 258 110 232 K95 98 95 270 240 60 T(oC) TDS (mg LK1) 1889 932 646 1064 1959 2241 2130 597 1341 1273 475 626 432 1561 455 366 528 638 2016 652 408 1470 1224 2943 470 601 1599 453 660 649 773 477 2102 2100 1127 485 1711 344 1451 2207 Na (mg LK1) 29 19 14 56 340 32 130 27 178 132 29 29 12 139 27 153 28 24 40 21 14 23 22 619 15 21 79 21 55 54 76 30 412 78 57 25 28 157 69 587 K (mg LK1) 1.2 1.3 0.5 2.0 5.0 2.0 5.8 1.5 3.6 2.2 1.1 2.3 0.9 4.1 1.0 1.7 1.7 1.2 1.8 1.3 0.9 1.2 1.0 6.8 0.9 1.1 3.2 1.2 1.0 1.1 1.1 1.0 16.0 3.1 11.4 1.3 2.2 2.4 5.9 23.0 Mg (mg LK1) 48 17 10 43 44 47 45 15 26 55 11 12 8 22 12 14 9 3 48 10 2 28 24 55 3 7 53 5 10 31 47 13 36 48 22 9 49 13 90 72 Ca (mg LK1) 520 205 122 168 250 580 552 106 174 190 84 120 92 343 86 38 103 168 602 151 93 350 301 352 101 123 404 96 125 81 83 89 323 595 258 98 510 34 224 111 NH4 (mg LK1) Cl (mg LK1) 855 240 86 151 1100 970 1070 44 359 261 45 47 21 780 26 32 34 116 1030 38 19 530 431 1330 32 90 750 31 93 80 250 43 1080 1065 356 29 830 44 247 1081 SO4 (mg LK1) 105.0 75.0 100.0 115.0 0.0 260.0 92.5 27.0 54.0 105.0 1.0 59.9 24.9 79.3 0.0 58.0 18.0 1.0 32.0 29.0 0.0 230.7 60.0 170.0 1.0 0.0 25.0 1.0 57.0 80.0 11.5 1.0 0.0 31.0 85.0 7.0 31.3 16.0 175.0 63.8 NO3 (mg LK1) 110.4 114.0 96.8 15.0 0.0 170.0 25.0 7.5 10.1 14.5 16.3 61.2 6.5 13.5 25.5 15.0 40.9 84.5 12.8 187.0 64.2 150.0 116.6 48.4 47.5 43.6 4.5 40.9 14.1 18.0 10.1 29.9 0.0 31.0 36.5 28.2 32.0 4.0 272.8 6.2 NO2 (mg LK1) 0.001 0.002 0.001 0.022 0.000 0.020 0.015 0.000 0.001 0.051 0.001 0.002 0.001 0.003 0.002 0.042 0.000 0.001 0.002 0.020 0.000 0.000 0.001 0.001 0.002 0.000 0.215 0.015 0.000 0.001 0.002 0.001 0.000 0.005 0.006 0.003 0.000 0.044 0.015 0.000 HCO3 (mg LK1) 211 254 210 510 220 181 210 360 531 512 280 296 267 181 277 365 286 234 245 206 207 157 262 353 261 308 278 250 298 299 289 261 235 245 299 283 220 427 367 263 0.05 0.04 0.08 PO4 (mg LK1) O2 (mg LK1) 8.9 7.8 6.5 4.5 0.0 Gypsum si K1.147 K1.443 K1.439 K1.356 K0.746 K1.202 K2.035 K1.681 K1.395 K3.520 K1.648 K2.084 K1.343 K2.130 K2.204 K3.313 K1.634 K1.894 K0.874 K1.466 K1.108 K3.435 K1.825 K3.457 K1.677 K1.719 K2.585 K3.504 K1.655 K1.355 K2.623 K1.669 K2.716 K1.180 K1.927 Calcite si Dolomite si K0.237 K0.367 K0.752 0.052 K0.592 0.248 K0.572 0.242 K0.968 K0.079 K0.219 K0.425 K0.604 0.692 K0.140 0.672 K0.121 K0.935 0.663 K0.306 K0.441 K0.156 K0.606 K0.545 K0.764 K0.087 1.106 K0.069 K0.358 K0.033 0.040 0.441 K0.399 0.039 K0.448 K0.103 1.394 0.419 1.680 0.110

W2 W4 W6 W8 W14 W15 W16 W19 W23 W28 W29 W32 W35 W39 W40 W43 W44 W46 W47 W48 W49 W57 W62 W64 W67 W68 W69 W70 W71 W72 W73 W74 W75 W76 W77 W78 W79 W80 W81 Mix

6.87 7.04 7.11 6.96 6.81 7.20 6.72 7.41 6.54 6.80 7.25 7.25 7.15 7.63 7.28 7.76 7.31 7.14 7.24 7.28 7.59 7.21 6.78 6.74 7.26 7.31 7.43 7.53 7.14 7.16 7.12 7.58 6.89 6.93 6.85 7.33 7.67 7.59 7.60 7.17

19.28 19.96 18.05 17.60 19.80 19.65 19.65 19.20 17.60 19.20 18.60 17.00 15.00 18.50 18.70 20.30 19.80 18.70 18.50 19.40 18.80 17.50 18.60 17.40 19.40 19.35 19.30 19.90 17.50 17.35 17.55 18.70 18.00 17.75 18.00 18.60 17.60 19.70 18.90

0.221 0.189 K0.006 0.198 K0.097 0.495 0.080 0.403 K0.197 0.094 0.150 0.170 0.067 0.769 0.187 0.380 0.291 0.223 0.702 0.259 0.416 0.296 0.070 0.003 0.214 0.390 0.816 0.439 0.188 0.017 K0.031 0.468 K0.045 0.388 0.136 0.293 1.027 0.250 0.862 K0.030

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0.010 0.090 0.890 0.000

0.04 0.06 0.09 0.07 0.02

9.1 5.9 7.0 7.1

0.650

0.05 0.04 0.03 0.03 0.02 0.04 0.03 0.03 0.05 0.02 0.02 0.02 0.03 0.04 0.03 0.03 0.07 0.00 0.04 0.04 0.06 0.04 0.03 0.09

0.7 8.0 6.5 4.7 8.0 7.0 6.6 7.1 7.9 7.9 2.1 7.8 7.1 5.3 6.3 9.5 0.0 4.4 3.6 4.8 8.3 2.2

0.450

0.900

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PHREEQC software was also used. According to Parkhurst et al. (1980), PHREEQC is a speciation code which by using the Mass Balance and electroneutrality equations, is capable of simulating geochemical reactions such as mixing of waters, addition of net irreversible reactions to solution, dissolving and precipitation phases to achieve equilibrium with the aqueous phase, and effects of changing temperature. Concentrations of elements, molalities and activities of aqueous species, saturation indices, and mole transfers of phases to achieve equilibrium can also be calculated. In this paper, calculations of molalities and activities of aqueous species were made using this code. The study of the evolution of ion exchange phenomena has been conducted by the use of the same code (Parkhurst and Appelo, 1999). Ion-exchange reactions are modeled following the Gaines-Thomas convention and equilibrium constants (Ki\j) derived from the databases distributed with the program (phreeqc.dat and wateq4f.dat). The saline end member composition, namely the mix water used in the model, was also calculated by assuming conservative mixing between seawater of the area and the fresher water W49. The quality

criterion for this sample was that it should have a ClK content equal to that of most saline groundwater that is very near to the sea. The mixing ratio used to calculate the mix composition was 5%. The recharge water corresponds to that of Mylois spring (W35) that is used for this purpose. Physical and chemical properties of all the water samples in the area are given in Table 1.

5. Results and discussion 5.1. Groundwater quality Intense agricultural activities, over pumping and fertilization, are reected to the groundwater quality. Fig. 2 shows the distribution of ClK and NOK 3 ions resulting from Surfer software using the kriging method. It is clear that over pumping led to an increase of ClK content (Fig. 2a) especially at the coast. Increased values are even observed inland where at Argos town the Cl concentration reaches 400 mg LK1. Although it is well documented that salinization of coastal aquifers may be due to several processes such as evaporitic salts present in the

Fig. 2. (a) Chloride distribution (mg LK1) in Argos Plain, autumn 2000. (b) Nitrate distribution (mg LK1) in Argos Plain, autumn 2000. Geological symbols are same as in Fig. 1.

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aquiferous materials, leaching from recent marine sediments saturated by brackish waters, and marine aerosols and marine intrusion (Pulido-Bosch et al., 1992; Sanchez-Martos et al., 1999), since 1965 the chemical evolution of the areas groundwater (Poulovassilis et al., 1996) undoubtedly indicates seawater intrusion. The wide application of fertilizers resulted to very high concentration of NOK 3 (Fig. 2b) and NH3 that surpass frequently the maximum admissible limits for drinking water (Directive 75/440/EU) (Table 1). The maximum concentrations occur at the eastward along the axis NafplionMidea where fertilization is very intense. The mean redox value (Eh, 223.7 mV) is elevated and, in combination with the dissolved oxygen concentration (DO, 6.08 mg LK1), indicates that the aquifer is under oxidizing conditions. This may be attributed to rapid replenishment of the groundwater, which is connected to intense pumping and articial recharge. In this way, ammonium from agricultural fertilizers is transformed into nitrate ions according to the reaction: 2NHC 4 C4O2/2NO3C2H2OC C 4H . Under these conditions, nitrates are transported as an inactive element (Freeze and Cherry, 1979; Antonakos and Lambrakis, 2000). However, in the coast, around samples W14 and 75, reducing conditions have been conrmed. Redox values were negative and the concentration of dissolved oxygen, sulfates and nitrates was zero.

5.2. Hydrochemical processes Classication and interpretation of the groundwater hydrochemistry was carried out using the Piper diagram. Most of the samples are classied into four major water groups. The water types of Ca2CHCOK 3 , and NaCHCOK (left side of the diamond in Fig. 3) 3 belong to the rst group, and the water types of NaC ClK and Ca2CClK (right side of the diamond) belong to the second. These groups show waters that take part in ion exchange phenomena (Lloyd and Heathcote, 1985). The water types of CaC2ClK and NaCHCOK 3 are identical to the salinization and freshening process that take place simultaneously due to ion exchange (Appelo and Postma, 1993). Groundwater subject to salinization are located in the central and southern parts of the plain where the process is in progress according to the equation: NaCC1/2CaX241/ 2Ca2CCNaX, where X is the exchanger. Groundwater subject to freshening are located at the periphery of the plain where articial recharge with fresh water supplies the groundwater with Ca2C according to the equation: 1/2Ca2CCNaX41/2Ca X2CNaC. Similar water types are very common in coastal areas in Greece (Lambrakis, 1997; Lambrakis et al., 1997a,b; Petalas, 1997; Petalas and Diamantis, 1999; Lambrakis and Kallergis, 2000). Effects of water-rock interactions with carbonate rocks were investigated by calculating calcite, dolomite and gypsum saturation indices. As shown in Fig. 4, most of the samples are saturated to dolomite, almost all samples are saturated to calcite, while all samples are under-saturated to gypsum. According to the paper of Plummer et al. (1990), in an aquifer containing dolomite and calcite one might expect that groundwater is close to equilibrium for both minerals. If gypsum also exists the increasing calcium concentration due to the dissolution to this mineral, causes calcite to precipitate. The carbonate concentration decreases as calcite precipitates and this provokes the dissolution of dolomite. This overall process is known as dedolomitization (Appelo and Postma, 1993). The described situation reported in the Madison aquifer which consists of limestone, dolostones and gypsiferous layers, is completely analogous, even to the range of saturation indices values, to the detrital aquifer of Argos, where the sediments having

Fig. 3. Piper diagram showing the groundwater chemical types of the study area.

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Fig. 4. Calcite, dolomite and gypsum saturation indices as a function of dissolved sulfate contant.

originated from the weathering of limestone, dolomite and neogene formations of the wider area, include the above minerals. In other similar cases dolomitization processes are encountered in the place of dedolomitization ones. Pulido-Laboeuf (2004) reported that dolomitization occurs in samples containing more than 40% of seawater. However, this is not the case for the Argos aquifer where the most saline samples at the coast contain about 5% of seawater. 5.3. Ion exchange phenomena Ion exchange phenomena are conrmed by the use of an ion balance based on the end member waters of the area, namely the mix water and the fresher water, by constructing scatter plots diagrams of ClK, NaC

and Ca2. It is assumed that all water samples in the area resulted by mixing of these end members. In Fig. 5, the dotted line represents the saline composition line where W49 is the sample of fresh water and mix is the sample of saline water. All samples on this line represent an ionic ratio similar to water of saline composition in a conservative mixing. Divergences from the lines could be attributed to ion exchange phenomena. In Fig. 5a, many samples of groundwater show an excess of calcium with respect to chloride ions indicating seawater intrusion because sodium is taken up by the exchanger, while Ca2C is released. In Fig. 5b, the decit of sodium relative to chloride obviously also indicates seawater intrusion, while the samples from which sodium is in excess relative to chloride, indicate the freshening process.

Fig. 5. Scatter plot diagrams showing relationships between major ions.

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Fig. 6. Hydrolithological section in the cross-shore direction of the Argos plain (1) clays, sands, marls, and pebbles undivided; (2) clay cover; (3) sand and pebblesaquifer; (4) neogene marl conglomerates; (5) borehole; (6) groundwater level (Giannoulopoulos, 2000).

6. Description of the argos transport model Multicomponent chromatography patterns can be easily studied in one-dimension ow using computer simulation programs. Such a program is the PHREEQC transport code (Parkhurst and Appelo, 1999). The aquifer of Argos is modelled in the crossshore direction (Fig. 6) in a theoretical chromatographic column containing thirtynine cells with a total length of 7700 m. The aquifer matrix has specic chemical properties such as the cation exchange capacity (CEC) that was calculated to be 4.31 meq(100 g)K1 using the empirical formula CEC[meq(100 g) K1 ]Z 0.7(%clay) C3.5(%C) of Breeuwsma et al. (1986). Dispersion was simulated by mixing cell contents at different time steps. A mixing factor, mix f Z DL DtDxK2 , controls which part of each cell mixes with two neighbouring cells. In the above equation, DL is the hydrodynamic dispersion coefcient (m2 sK1), Dt is the length of the time step, and Dx is the cell length. During each time
Table 2 The model information and input data Hydrolithology Alternatives aquifers beds with coarse clastic material and silty clays Hydraulics characteristics TZ7261425 m2 dK1, LZ7. 7 km, BZ56 m, qmZ0.23, qimZ 0.05, aLZ200 m

step, water is batchwise transported to the next cell and equilibrated with the aquifer matrix. With molecular diffusion assumed to be negligible, DLZaLv, where aL is the dispersivity coefcient, and v is the pore water ow velocity. The mixing cell concept is essentially a nite difference solution of the advection-reaction equation (Bajracharya and Barry, 1993). Based on the concept of piston ow of solution through the cells, the time the solution resides in any one cell can be derived from the equation DtZDxvK1, where v is ow velocity. Table 2 summarizes the characteristic magnitudes of the aquifer and all necessary data needed for the simulations. All values in this table correspond to eld conditions except for immobile porosity (qim). Dispersivity values were obtained using Gelhar et al. (1985) diagram. 6.1. Salinization phenomena In a rst case, progress of the saline front caused by intense pumping is studied. The water entering the

The end members chemical analyses (mmolkgK1) Mix water K Ca2C: 2.77, Mg2C: 2.98, NaC: 25.5, KC: 0.58, HCOK 3 : 4.31, Cl : K1 K K 30.49, SO2 : 0.66, NO : 0.0, pH: 7.17, CEC: 4.31 meq(100g) 4 3 Recharge water, W35 K Ca2C: 2.29, Mg2C: 0.21, NaC: 0.52, KC: 0.02, HCOK 3 : 4.95, Cl : K K 0.36, SO2 :0.24, NO : 0.17, PH:7.15 4 3

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aquifer from the fresh water-sea water transition zone is assumed to have an almost constant chemical composition similar to that of mix water. Data from chemical analyses ions concentrations as well as from the model running plotted against the distance from the shore of the saline frond. As shown in Fig. 7(ac), there is a good coincidence between the modeled and experimental curves, therefore the simulation approach can be accepted. This coincidence was observed only when the dual porosity modelling ability of the code was used and the immobile porosity was set to 0.05. That is done under the assumption that the aquifer system presents properties of a medium of dual porosity, where exchanges of chemical species take place between owing and stagnant water through the process of diffusion. It should been accepted that dual porosity is the usual case for the alluvial coastal aquifers as clay materials that favor stagnant conditions are always present in the sediments at depth (Petalas, 1997). An increase in calcium and magnesium concentration is followed by a decrease of sodium. This is due to ion exchange mechanisms between these elements. Chromatographic patterns during the salinization process are obvious. For calcium and magnesium ions, concentrations were even higher than those originally presented in the brackish water at a mid-distance from the shore. Calcium and magnesium were taken up by the aquifer matrix and exchanged with sodium. During this time, the brackish water with a NaCl water type, becomes the CaCl2 water type. Sodium compensates the release of calcium and magnesium and the concentration of these elements reaches new levels. The simulated concentrations of groundwater are similar with levels of analysed groundwater concentrations after 15 shifting of the column water that corresponds to 0.4 pore volumes. At the end of the column, concentrations of chloride, sodium and potassium ions are almost constant. 6.2. Freshening phenomena In a second stage the simulation of freshening phenomena has been made based on the previous model tested parameters. During earlier studies, (Lambrakis, 1997; Kallergis et al., 1997; Lambrakis and Kallergis, 2000), freshening process under natural

Fig. 7. Variation of ion concentrations as a function of the distance from the sea (cross-shore direction) at the end of the simulation period.

N. Lambrakis / Journal of Hydrology 323 (2006) 230243

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Fig. 8. Elution of exchangeable cations adsorbed on salt water sediments with fresh water solution of Argos aquifer. Second gure is the rsts continuity. Note the different scale of the Y-axis.

recharge conditions in some alluvial coastal Greek aquifers was calculated to be very belated. The freshening time or rehabilitation time, was estimated to be some hundred of years. In all above cases chromatographic patterns were obvious. Their intense depended on CEC, while the dispersivity exercised only a secondary role, obvious on the column breakthrough but not seriously inuenced the rehabilitation time. Fig. 8(a and b), describes chemical variations at the end of the column (near the shore), occurring from the beginning of the recharge period until the groundwater has the chemical characteristics of the recharge water. The ion exchange and chromatographic patterns, presented in this gure, have already been described in Valocci et al. (1981a), and Beekman and Appelo (1990). There is an abrupt decline of the concentrations of almost all ions due to their dilution after the salinity front. Calcium and magnesium were taken up by the matrix while sodium was released, and during this time fresh Ca(HCO3)2 type water becomes NaHCO3 type water. After the initial decrease period, which for both calcium and magnesium corresponded to the displacement of one pore volume, (Fig. 8a), the concentration of these ions remain very low, under the recharge water concentration, for a long period that corresponds to 27 pore volumes. For this period the decit of the above-mentioned ions concentrations of the groundwater relatively to the fresh water concentrations are balanced with a surplus on sodium that are eluted from the sediments. After that period, the concentrations of these ions increase and are

comparable with those of the fresh water (Fig. 8b). The magnesium concentration, in particular, surpasses that of the recharge water because calcium from recharge water exchange magnesium from the exchanger, during and after the release of sodium. Chloride ions, employed in this study in a similar fashion with nitrate ions which are not shown on the gure because they are inactive in the conditions of the examined aquifers, are ushed out and removed from the aquifer during the replacement of one pore-volume. Therefore, partial restoration of the aquifer is accomplished in a short time relatively to the complete rehabilitation that takes place very long time. Dispersivity values used in the entire running of the model inuenced imperceptibly the rehabilitation time. The parameters that inuenced mainly the solution of this kind of problems were the initial and boundary conditions as well as the porosity of the materials and the content of clay minerals closely related with CEC.

7. Conclusions The chemical composition of the groundwater in the heterogeneous conned alluvial coastal aquifers of Argos resulted from dissolution of minerals and ion exchange. Chromatographic patterns are always developed in a profound way during saline water or fresh water displacement due to freshening or to salinization process, respectively. The different water types are easily separated using chemical diagrams as

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the Piper diagram. The dominate displacing cation, which is usually sodium in the case of salinization or calcium in the opposite case of freshening, is discerned by the use of a simple chemical balance based in the concervative mixing of two end members waters samples from the study area. The variation in the concentration of the exchangeable ions, depends mainly on the CEC and the porosity of the aquifers sediments and is also closely related to the amount of the displaced water. Salinization or freshening phenomena are easily simulated with the use of the PHREEQC code. The use of this code has approved that the simulated results could be similar to that obtained in the laboratory if one assume that part of the aquifer water is mobile and ows along the connected porosity, while another part remains immobile or stagnant within the structural units. Exchange of water and solutes between the two parts may occur through diffusion. This is true, given that in this type of aquifers clay minerals are always present in signicant proportion. Mobile porosity can be in situ determined as well as CEC. Difculties arise for the estimation of immobile porosity. Successive running of the code allows for an estimation of this, given that all the rest substantial parameters can be easily determined in eld and the laboratory. Small variations in the estimation of the dispersivity values do not affect the results. Salinization, is a relatively fast process. Freshening time period is also a fast mechanism, in the case of partial restoration of the aquifer. The complete restoration is practically impossible because it demands very large amounts of ushing water and consequently very long period of time.

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