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Natural Resources Research, Vol. 9, No.

2, 2000

Multivariate Statistical Analysis in the Assessment of Hydrochemistry of the Northern Korinthia Prefecture Alluvial Aquifer System (Peloponnese, Greece)
K. Voudouris,1 A. Panagopoulos2,3 and J. Koumantakis2
Received 21 December 1999; accepted 14 February 2000

The application of multivariate statistical analyses of hydrochemical data has proved to be most successful in the assessment of groundwater hydrochemistry, especially in situations where numerous samples are available. Fifteen (15) hydrochemical parameters were considered (pH, E.C., T.D.S., T.H, Ca, Mg, Na, K, HCO3, Cl, SO4, NO3, NO2, NH4, PO4) in 131 samples collected from the alluvial aquifer of NE Korinthia, during May 1997. Simple and multiple regression, factor, and trend-surface analyses were applied in order to examine the importance of each parameter, investigate correlations among them, and separate them into groups. Statistical factors were selected and their geographical distribution was mapped. It was concluded that use of such methods reveal the prevailing evolutionary mechanisms of the studied system, thus enabling accurate and relatively quick hydrochemical assessments.
KEY WORDS: Hydrochemistry; hydrogeology; multivariate statistical analysis; Greece.

INTRODUCTION The coastal part of the northern Korinthos prefecture is characterized by increasing trend in water consumption, as a result of intense urbanization, tourist development, and irrigated land expansion. Regional water needs are covered mainly by groundwater abstracted from the alluvial aquifer via numerous wells and boreholes and partly by winter surface runoff of the Asopos River, which is located on the western edge of the studied region (Fig. 1). Complete lack of a rational water-resources management scheme in the studied alluvial aquifer system has resulted in significant groundwater quality deterioration and in the establishment of negative water balance (Panagopoulos,

Section of Hydrogeology, Department of Geology, University of Patras, Patras, Greece. 2 Section of Applied Geology, Department of Mining and Metallurgical Engineering, National Technical University of Athens, Heroon Polytechniou 9, 15780, Athens, Greece. 3 To whom correspondence should be addressed. (e-mail: mmgpap@central.ntua.gr)

Koumantakis, and Stavropoulos, 1999). The region studied is located between N37 55 and N37 59 latitude and E22 44 and E22 55 longitude. Study and interpretation of groundwater chemistry is enhanced significantly by the use of multivariate statistical analysis, especially when a large number of samples is available. During the last decades, these methods have been applied systematically by numerous researchers in an attempt to interpret various hydrochemical problems (Douglas and Leo, 1977; Seyhan, Van de Griend, and Engelen, 1985; BrizKishore and Murali, 1989; Ruiz, Gomis, and Blasco, 1990; Rao, Reddy, and Nayudu, 1996, Jayakumar and Siraz, 1997, Buccianti, 1997; Voudouris and others, 1997; Daskalaki and Voudouris, 1997; Chen and others, 1997; Papatheodorou and Lambrakis, 1997; Ratha and Venkataraman, 1997). Simple and multiple regression analysis, factor analysis, and trend-surface analysis were used in the framework of this study on hydrochemical data of 131 groundwater samples collected from the northern coastal alluvial aquifer system of the Korinthos Prefecture, southern Greece. These methods were employed
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1520-7439/00/0600-0135$18.00/0 2000 International Association for Mathematical Geology

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Figure 1. Geological map study area.

in order to determine the prevailing groundwater hydrochemical evolution mechanisms on a regional scale. Statistical analyses complemented the conventional study of simple hydrochemical maps and clarified results that were occasionally ambiguous or even contradicting. This was a result of either local or borehole scale exhibited anomalies in the measured and calculated hydrochemical parameter values or of simultaneous existence of more than one hydrochemical processes in the same part of the studied region.

GEOLOGICAL STRUCTURE AND HYDROGEOLOGICAL SETTING The plain, north of the national highway, is formed of Recent unconsolidated material consisting of sands, pebbles, breccias, and fine clay to silty sand deposits, characterized by high degree of heterogeneity. Lateral continuity of the previously described deposits is disrupted by Recent and older fluviotorren-

tial deposits originating from the streamsrivers that flow across the studied region (Fig. 1). South of the national highway, which bounds the study region, the Tyrrhenian deposits of coastal origin crop out. Usually, they consist of highly consolidated breccio-conglomerates, sand, small-size gravel, and sporadically marl intercalations. It is believed that these deposits are expanding to the north locally, underneath the Recent unconsolidated deposits of the plain. Their outcrop is disrupted as a result of erosion. The Pliocene deposits of the marl series occupy most of the hilly region farther south of the region. Within this formation, sandstone, consolidated gravel, conglomerates, and marly limestones of lacustrine origin exist in locally restricted intercalations. The groundwater resources in the area studied are located within the coastal aquifer system, which consist of the described Recent deposits. A fault zone along the national highway delineates the southern edge of the aquifer system, which is bounded by the Gulf of Korinthos to the north. To the east, the system

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is bounded by the Thyrrenian deposits extension to the sea (approximately 2 km west of the city of Korinthos), whereas to the west, it is bounded by the outcrop of the marl series, by the city of Kiato (Fig. 1). The marl series, which, as an entity, is considered an aquitard, slopes to the north and forms the bedrock of the studied coastal alluvial aquifer system (Panagopoulos, Koumantakis, and Stavropoulos, 1999). The thickness of the plains deposits ranges from 30 m to 70 m, whereas along the fluviotorrential deposits of the Asopos River it exceeds 100 m. As a result of their origin, the deposits are characterized by high degree of heterogeneity and anisotropy. This also was documented from the study of lithological sections of boreholes drilled in the region and the pumping test analyses conducted in some of them (Koumantakis and others, 1999). Despite the exhibited heterogeneity, however, it can be stated that on a regional scale there is a progressive transgression from coarse material in the south to fine material in the north. On the contrary, abrupt lithological changes from coarse to fine material

are observed moving from the contemporary river courses to the areas in between. Anisotropy is extended to the vertical scale as well, where typically sand, clay, silt, and gravel interchanges and mixtures are observed in various thickness intercalations. The system consists of an unconfined phreatic aquifer superimposed on successive confined or semiconfined aquifers. Because of the heterogeneity, these aquifers either are delimited by lateral lithological transitions or extended into an adjacent unit. In parallel, within the secluded Thyrrenian conglomerate blocks overhanging aquifers of low potential may develop. As a result of the described geometry, a number of distinct aquifer units of local significance and small extent have developed and are evidenced by the observation of varying piezometric heads in adjacent wells and boreholes. Despite the documented heterogeneities, however, it is suggested that on a regional scale a uniform aquifer may be considered on the basis that observed lithological anomalies are not extensive and most groundwater level measurements are indicative

Figure 2. Groundwater sampling locations.

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of a single piezometric surface (Koumantakis and others, 1999). Recharge to the aquifer system originates from direct infiltration of precipitation and riverbed infiltration. Lateral inflow from the fluviotorrential deposits, especially those of the Asopos River, and also from the Tyrrhenian deposits across the southern edge of the basin is essential to the systems replenishment. It has been demonstrated that returns from flood irrigation, which traditionally is practiced during springtime in the region, play a major role to aquifer recharge. Groundwater overexploitation, being practiced by abstractions from about 1000 wells and boreholes, has resulted in significant head decline that exceeded 2.0 m during hydrological year 19971998 (Koumantakis and others, 1999). Consequently, a large number of wells located upstream in the south zone of the system have been temporarily or permanently incapacitated, negative water balance is established, groundwater deterioration has emerged, and extensive saline water intrusion has started (Panagopoulos, Koumantakis, and Stavropoulos, 1999). Indicative of the extent of groundwater deterioration, is that in most of the areas, it is not suitable for human consumption, and in considerable areas it is marginally acceptable even for irrigation use (Koumantakis and others, 1999; Panagopoulos, Koumantakis, and Stavropoulos, 1999).

with the calculated ionic balance error for each sample (as suggested by Appelo and Postma, 1993). The calculated mean value (), maximum and minimum values, standard deviation (), and coefficient of variation (/ ), were calculated for each chemical variable, and are quoted in Table 1. The coefficient of variation is considered an index of the relative dispersion of each variable. As earlier noted, available data consists of a relatively large number of analyzed samples (131) and considered parameters (15). It therefore was decided that these parameters should be analyzed within the framework of a multivariate system that divides them into groups and reveals possible relationships between them. In this way, the large data set is reduced to a small number of factors that are easier to evaluate in order to deduce the main hydrochemical processes. Resultant factors consist of highly intercorrelated variables, where each factor represents a specific hydrogeochemical process that actually has formed the variables fluctuation percentage. Thus, application of multivariate statistical analysis reduces the complexity of the problem without any significant loss of information. This study utilized regression, factor, and trendsurface analysis.

RESULTS OF STATISTICAL ANALYSES AVAILABLE DATA AND APPLIED METHODS As part of the groundwater hydrochemical study carried out, an extensive sampling program was performed in May 1997. A dense network consisting of 131 points spread over the studied region was designed (Fig. 2), in order to obtain representative samples of the entire aquifer system. The equipment of the National Technical University of Athens, Section of Geological Sciences, facilitated laboratory determinations. In situ measurements included electrical conductivity (E.C.), pH, and water temperature. Determinations of ion concentrations were carried out using the following methods: colorimetric titration for Cl and HCO3, atomic absorption for Ca2 and Mg2, flame photometry for K+ and Na+ and spectrum photometry for SO42, NO3 NO2, NH4+, and PO43 (following the procedures described by Greenberg and others, 1985). Based on the ion determinations, total hardness, alkalinity, and total dissolved solids were calculated. Quality of the performed determinations was checked The calculated coefficients of variation (Table 1), indicate wide distribution of NH4+, K+, Na+, Cl, and NO2 and limited distribution of SO42, NO3, and PO43. A study of the same table leads to the following conclusions. The mean pH value denotes alkaline groundwater character. Electrical conductivity values (E.C.) range between 550 S/cm and 4,120 S/cm, the highest being related to seawater intrusion. Likewise, the mean total dissolved solids (T.D.S.) value is as high as 954 mg/L, and exhibits a relatively large standard deviation, thus indicating considerable fluctuations around the mean value. Based on calculated total hardness values (T.H.), most groundwater samples are characterized as very hard (T.H. 300 mg/L of equivalent CaCO3). Mean nitrate concentration also is high at 73 mg/ L and is attributed to intensified agriculture activities linked with overfertilization during the last decades. About 75% of the examined samples exceeded the maximum admissible concentration of 50mg/L set by the European Union (E.U. Council, 1998), for water intended for human consumption.

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Table I. Statistical Characteristics of Considered Parameters, as Deduced by Results of Performed Hydrochemical Analyses of 131 Samplesa Value Parameter PH E.C. (S/ cm) T.H. T.D.S. Ca2 Mg2 Na+ K+ HCO3 Cl SO42 NO3 NO2 NH4+ PO43
a

Mean () 7.16 1328 669 954 165 65 88 9.5 483 97 216 73 0.04 0.32 0.152

Min 6.68 550 94 340 31 16 19 1.0 268 15 0.1 0.3 0.0001 0.0 0.05

Max 8.05 4120 1782 3041 285 290 440 130 929 694 860 285 0.45 8.0 0.70

Stand. deviation () 0.31 568 226 398 43 42 85 20 89 119 141 49 0.063 0.96 0.09

Coefficient of variation (/) 0.04 0.42 0.33 0.42 0.26 0.64 0.96 2.1 0.18 1.22 0.65 0.67 1.57 3.0 0.59

Where applicable, values are in mg/L, unless otherwise stated.

Correlation Analysis A widely used correlation criterion between two variables is the simple correlation coefficient, which indicates the sufficiency of one variable to predict the other (Davis, 1986). This coefficient is used to determine correlation between the variables when the dependent (x) is only influenced by the independent (y) and vice versa. Despite the fact that this does not apply to hydrochemical data, simple correlation coefficient is being used as a measure to describe a relationship between two variables. Three different correlation type generally are identified in aqueous systems (Douglas and Leo, 1977; Rao, Reddy, and Nayudu, 1996), namely: (i) a strongly competitive correlation between ions of the same charge, but different valence number; (ii) a strong chemical association between ions of opposite charge, but equal valence number; and (iii) a noncompetitive correlation between ions of the same type of charge and equal valence number. The correlation coefficient matrix between the examined ions, which was calculated using linear regression analysis, is illustrated in Table 2. Study of this matrix concluded the following. Ions of the same type of charge and different valence number A relatively strong but not significant correlation between Mg2 and Na+ is observed (r 0.58). A negative and statistically insignificant correlation is exhibited between Ca2 and Na+, K+

(r 0.22 and, 0.19, respectively), whereas SO42 have a correlation coefficient of r 0.55 with Cl and r 0.46 with NO3. Ions of opposite charge and equal valence number Strong correlations are indicated between Na+ and Cl (r 0.84), Mg2 and SO42 (r 0.80), Ca2, and SO42 (r 0.60), HCO3 and Na+ (r 0.70), with weaker correlations between K+ and Cl (r 0.50) and K+ and NO3 (r 0.30). Ions of the same type of charge and equal valence number Correlation between Ca2 and Mg2 is not significant (r 0.26) and likewise between NO3, HCO3, and NO2. Moreover, correlation between Cl and NO3 is relatively weak (r 0.54), as it is between Na+ and K+ (r 0.47). As deduced from the correlation coefficient matrix (Table 2), the value of electric conductivity (E.C.) mainly depends upon the major ion concentrations (Ca2, Mg2, Na+, K+, HCO3+, Cl, SO42, NO3). Under the assumption that E.C. is solely a function of the major ion concentrations, the multiple regression model was applied between E.C. and the ion concentrations expressed (in mg/L), as follows in Equation (1): E.C. b0 b1 Ca b2 Mg b3 Na b4 K b5 HCO3 b6 Cl b7 SO4 b8 NO3 (1) where E.C. is the electric conductivity of the sample

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Table 2. Correlation Coefficient Matrix of Considered Parameters Ca2 Ca2 Mg2 Na K HCO3 Cl SO42 NO3 NO2 NH4+ PO43 E.C. T.D.S. pH T.H. 1.00 0.26 0.22 0.19 0.17 0.02 0.60 0.42 0.28 0.37 0.39 0.65 0.29 0.43 0.64 Mg2 Na+ K+ HCO3 Cl SO42 NO3 NO2 NH4+ PO43 E.C. T.D.S. pH T.H.

1.00 0.58 0.26 0.34 0.80 0.80 0.58 0.05 0.07 0.11 0.86 0.91 0.33 0.90

1.00 0.47 0.70 0.84 0.49 0.26 0.02 0.29 0.59 0.88 0.78 0.55 0.34

1.00 0.10 0.50 0.17 0.30 0.02 0.02 0.63 0.56 0.56 0.36 0.10

1.00 0.40 0.35 0.03 0.03 0.35 0.37 0.64 0.40 0.15 0.21

1.00 0.55 0.54 0.04 0.09 0.47 0.93 0.87 0.58 0.60

1.00 0.46 0.15 0.17 0.03 0.76 0.83 0.02 0.90

1.00 0.14 0.14 0.14 0.58 0.61 0.18 0.61

1.00 0.17 0.06 0.09 0.07 0.06 0.12

1.00 0.35 0.06 0.00 0.19 0.22

1.00 0.19 0.28 0.42 0.09

1.00 0.97 0.43 0.74

1.00 0.35 0.84

1.00 0.06

1.00

(S/cm at 25C) and b0, . . . , b8 are the equations parameters. Application of the model described in Equation (1), yielded: E.C. 141 0.61 Ca 1.07 Mg 1.35 Na 1.52 K 0.85 HCO3 2.14 Cl 0.87 SO4 1.25 NO3 (2) The calculated multiple correlation coefficient is as high as 0.99, standard error is 72.4, and R-square is 0.98, thus indicating the model accounts for 98% of the observed distribution according to criteria set by numerous researchers (Chatterjee and Price, 1991; Bora-Senta and Moisiades, 1997). The F ratio is considerably larger (658) than the critical F12, 118, 0.005 value of 2.54, which is retrieved from reference matrices. In the compiled model, every major ion contributes significantly, which, coupled with the results, leads to the conclusion that it is capable of forecasting the dependant variable (E.C.) values. Substituting the calculated major ion concentrations of a representative sample into Equation (2), the percentage by which each ion contributes to the E.C. value was determined to be: Cations: Ca2 12.1%, Mg2 4.8%, Na+ 9.6%, K+ 1.4% Anions: HCO3 36.7%, Cl 12.3%, SO42 14.9%, NO3 8.2% It, therefore, follows that given the electrical conductivity value of a groundwater sample from the

region: its major ion concentrations may be determined based on the percentages as mentioned. It has to be stressed, however, that acceptable results can be expected only if the method is applied to E.C. measurements conducted in the same season as the sampling program on which the produced model is based, in order to ensure as high compatibility as possible to the prevailing hydrochemical evolution mechanisms within the studied aquifer system at that time.

Factor Analysis This type of analysis was applied in order to reduce complexity of the initial data matrix by producing a small number of factors that explain a large amount of the total variance of the raw data. Hence, factor analysis leads to the establishment of subgroups of closely interrelated elements aiming at interpreting hydrochemical evolution mechanisms. The R-mode factor analysis has been applied on hydrochemical data by a number of researchers and comprises the following steps (Saager and Esselaar, 1969; Briz-Kishore and Murali, 1989; Ruiz, Gomis, and Blasco, 1990; Voudouris, 1995; Voudouris and others, 1997): Data standardization, so that mean value is zero and standard deviation is one for every variable (Davis, 1986). This step is essential, as computation of the correlation coefficient matrix requires normal distribution of all variables (Jayakumar and Siraz, 1997). Next, the correlation coefficient matrix is solved, the eigenvalues are calculated, and the factors

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Table 3. Loadings of Varimax rotated Four-Factor Model and Communality Values CommuFactor I Factor II Factor III Factor IV nalities 0.56 0.91 0.62 0.19 0.34 0.70 0.92 0.49 0.09 0.18 0.00 0.97 0.16 0.92 0.85 45.1 0.52 0.19 0.46 0.80 0.08 0.59 0.11 0.52 0.04 0.48 0.79 0.09 0.63 0.30 0.42 21.1 0.41 0.08 0.56 0.14 0.83 0.21 0.00 0.39 0.03 0.50 0.30 0.10 0.36 0.19 0.26 9.0 0.03 0.06 0.06 0.08 0.14 0.02 0.07 0.13 0.96 0.47 0.10 0.06 0.32 0.01 0.04 6.7 0.76 0.88 0.92 0.71 0.83 0.89 0.87 0.68 0.94 0.73 0.72 0.96 0.65 0.99 0.97

Variables Ca2 Mg2 Na+ K+ HCO3 Cl SO42 NO3 NO2 NH4 PO43 T.H. PH T.D.S. E.C. Variance (%)

that are correlated with eigenvalues greater than 1 are selected (Kaiser, 1958). The factors axes then are rotated to new positions in order to achieve more accurate interpretation of the results, on the basis of the varimax criterion (Voudouris and others, 1997). The factors loadings, which consist of their elements, form practically an assessment of the similarity degree between the variables and the factors. Applicability of the method is assured by the communality values of the variables, which in fact are a sufficiency measurement of how a group of factors describes the fluctuation of a variable. In an accredited application of factor analysis, the value of communalities for each variable should be close to 1 (Ruiz, Gomis, and Blasco, 1990). Finally, the factor scores were calculated, that is, the influence each factor has on the sampling locations. These values relate to the intensity of the chemical processes each factor represents. Extreme negative values (1) reflect regions not affected by the specific processes each factor represents, in contrast with positive values (1) that indicate areas under the influ-

Figure 3. Distribution of factor I scores.

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Figure 4. Distribution of factor II scores.

ence of the processes (Jayakumar and Siraz, 1997; Briz-Kishore and Murali, 1989). The R-type factor analysis was applied here in order to reduce the large hydrochemical database (131 samples), organize data into groups of similar characteristics, identify the weight of each parameter, and detect correlations between them. Application of the R-type factor analysis concluded with the selection of four factors, which explained 82% of the total variance. For each factor, its influence to the sampling location was determined by calculating its score. The eigenvalues of the four selected factors are 6.76, 3.16, 1.35, and 1.01, respectively. The concluded factor loadings after rotation are given in Table 3, whereas in Figures 36 the geographical distribution of the factors based on their values is illustrated. Study of these maps may indicate the importance of each hydrochemical process as represented by the selected factors, with reference to their geographical distribution. Values of communalities range between 0.65 and 0.99, thus indicating that selected factors adequately represent the entire range of variables fluctuations.

The first factor accounts for 45.1% of the total variance of the database. It is addressed as the salinity factor, because of exhibited high loadings on T.H. (0.97), SO42 (0.92), T.D.S. (0.92), E.C. (0.85), Cl (0.70), and Na+ (0.62). This factor is correlated to seawater intrusion of the coastal aquifer system, which results to the observed high values of the considered parameters. As deduced from the geographical distribution of the factors values (Fig. 3), the coastal area between Lecheo and Assos is characterized by high values, in contrast with the area around the communes of Poulitsa, Velo, and Vochaiko, where the values are negative. It is therefore indicated, that the former region is influenced strongly by seawater intrusion. Factor II accounts for 21.1% of the total database variance. It shows high loadings on K+ (0.80) and PO43 (0.79) and relatively high loadings on NO3 (0.52) (Fig. 4). Potassium concentration in seawater is higher, however, because K+ as a parameter is not included in the first factor and its correlation to Na+ and Cl is relatively low (r 0.47 and r 0.50, respectively) as quoted in Table 2, it is concluded that

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Figure 5. Distribution of factor III scores.

this second factor is related to mixed-type fertilizers that contain nitrogen, phosphate, and potassium (NPK). Study of the geographical distribution of factors values suggests that high values are concentrated in the Ancient Korinthos region, as well as in the southern part of Lecheo commune and the greater Vrachati area, where extensive application of fertilizers to cultivation is known to be practiced. Factor III exhibits high loadings with respect to HCO3 (0.83) and accounts for 9% of the total variance (Fig. 5) Bicarbonates, which prevail in freshwater, are related to soil carbon dioxide dissolution and dissociation of the unstable form of carbonic acid. Strongly positive values of this factor are exhibited in the areas of Kato Assos and Vrachati and slightly positive values in the area of Poulitsa. The observed negative values of this factor at the communes of Krines and Moulki are attributed to low carbon dioxide dissolution potential. Factor IV accounts for 6.7% of the total variance and exhibits high loadings with respect to NO2 (0.96). Nitrites are a relatively unstable intermediate form of

ammonium nitrogen oxidation. They are formed of bacteria-induced oxidation of organic nitrogen released from decaying fauna and flora, as well as from microbial-induced partial denitrification in environments characterized by oxygen depletion. High values of this factor are depicted in the areas of Kato Assos, Velo, Evagelistria, and Perigiali, whereas negative values are exhibited at the communes of Poulitsa, Kokkoni, and Krines (Fig. 6)

Trend-Surface Analysis Trend-surface analysis is a simple multiple regression technique where independent variables are based upon X and Y coordinates. This method attempts to generate a good fit surface expressed by an equation. To do so, the dependent variable Z is described as a function of its geographical location. The so-called trend surface can be either planar or curved. Trendsurface analysis allows for two-part separation of surface distribution (Chen and others, 1997):

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Figure 6. Distribution of factor IV scores.

Ho Ht Hr E where Ho observed value, Ht trend value, Hr residual value, and E random error. The random error value can be low and thus omitted. According to Watney (1985), trend values represent regional trends of the parameters distribution, whereas residuals represent local anomalies. Hence, conclusions can be drawn regarding the reasons that have formed the surface distributions, although in parallel, similarities and differences between various surface distributions can be examined on the basis of credible statistical criteria. In this paper, a third-degree (cubic) trend surface was computed in order to study the areal distribution of chloride ion concentrations through which seawater intrusion zones in the study area were delineated. The cubic trend surface is represented by a saddle-shaped surface, described by the following equation: Z a bX cY dX 2 eXY f Y2 gX 3 hX 2Y iXY 2 jY 3

where Z, chloride ion concentrations (mg/L), X, Y geographical coordinates, and a, b, c, d, e, f, g, h, i, j constants. To determine the credibility of the aforementioned equation, the R2 coefficient was calculated using the following equation (Papatheodorou and Lambrakis, 1997), and was 0.73: R2 (VarZ VarZr)/VarZ where VarZ variance of the initial data Z values and VarZr residuals variance. Study of the chloride concentration trend map, as illustrated in Figure 7, indicates the following. High chloride concentrations are depicted in the coastal region between Vrachati and Ancient Korinthos. More specifically, the highest values (above 300 mg/L) are observed in the areas of Lecheo and Ancient Korinthos communes. This region coincides to the geographical distribution of factor I, which, as earlier described in the performed factor analysis, is indicative of seawater intrusion. A gradual decline of chloride concentrations

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Figure 7. Chloride concentration equal trend curves.

from this saline zone to the southwestern part of the studied region (Krines Commune) is observed. The latter area is not influenced by seawater intrusion and chloride concentrations there are lower than 40 mg/L.

CONCLUSIONS Groundwater in the studied region seems to be hard to very hard, as total hardness expressed in CaCO3 usually exceeds 300 mg/L Nitrate concentrations are high over the region, having an average value of 73 mg/L. These concentrations are attributed to the agricultural practices of the region, under which intensive cultivation is carried out, supported by excessive application of NPK type fertilizers, where flood irrigation is applied. A significant correlation between Na+ and Cl, 2 Mg and SO42, HCO3 and Na+ is depicted, whereas correlation between Cl and NO3, Ca2 and SO42, K+ and Cl, Mg2, and Na+ seems to be lower. Applica-

tion of multiple regression analysis suggested that electric conductivity may be described properly as a function of major ion concentrations, hence, by measuring it in the field, major ion concentrations can be determined. It has to be stressed, however, that valid calculations rely upon electric conductivity measurements conducted over the same period as the sampling on which the equation derivation was based. Should hydrochemical evolution of the system become altered, it is believed that the derived equation will not be valid. Application of the R-type factor analysis, resulted in four factors which adequately describe 82% of the total data variance and are having the following loadings: (I) T.H., SO42, T.D.S., Mg2, E.C., Cl, and Na+; (II) K+ and PO43; (III) HCO3; and (IV) NO2. Factor I is related to seawater intrusion, factor II to application of fertilizers, factor III to groundwater carbon dioxide dissolution potential, and factor IV to the aquifer oxidation potential and the existence of organic matter within the aquifer matrix. Finally, application of trend-surface analysis revealed a seawater intrusion

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zone extending between Vrachati and Ancient Korinthos. Application of multivariate statistical analysis on 131 samples collected from the alluvial aquifer system of the northern coastal zone of Korinthos Prefecture, southern Greece, helped to delineate the major hydrochemical processes that control hydrochemical evolution of the region. It was concluded that such statistical methods may augment conventional hydrochemical analyses, by defining processes and trends indicated by the latter, but not clearly proved for a number of reasons that may include random errors during sampling, analyses, or even resulting from irregularities attributed to localized geological, or hydrodynamic particularities. It seems that statistical analyses are useful in situations where large data sets of wide areal distribution are to be considered jointly in order to deduce reliable results on regional groundwater hydrochemical evolution.

ACKNOWLEDGMENTS Raw data used in this paper were collected as part of a regional research project titled Hydrogeological feasibility study of artificial recharge application on the alluvial aquifer system of the northern Korinthos Prefecture, southern Greece. This project was funded by the Greek Ministry of Agriculture and elaborated by the research team of the Section of Geological Sciences, National Technical University of Athens, under the guidance of Prof. J. Koumantakis. Sampling was carried out by Mr K. Markantonis geologist and laboratory determinations were performed by Ms. E. Grigorakou mining engineer, to both of whom the authors extend their thanks. Finally, Ms. M. Hionidi is acknowledged for the preparation and editing of the figures used in this paper.

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