Environ Earth Sci (2012) 66:18711880 DOI 10.

1007/s12665-011-1411-3

ORIGINAL ARTICLE

Urban impacts analysis on hydrochemical and hydrogeological evolution of groundwater in shallow aquifer Linares, Mexico
Alberto Da vila Po rcel He ctor De Leo n Go mez Rene th Christoph Schu

Received: 8 December 2010 / Accepted: 6 October 2011 / Published online: 1 November 2011 Springer-Verlag 2011

Abstract In northeast Mexico is Linares City, which has an extensive agricultural area and many industrial activities. Near this city is the Cerro-Prieto Dam (*12 km NE direction); this drinking water reservoir captures the water of the Pablillo River catchment area and constitutes an important source of potable water for the metropolitan area of Monterrey, the largest urban center of this region. Groundwater sources in this area provide drinking water to Linares inhabitants. A hydrogeological and hydrochemical study was conducted on the shallow aquifers surrounding the urban centers (Linares and Hualahuises) to determine the evolution of the water quality between 1981 and 2009. The hydrochemistry was assessed upgradient and downgradient from the potential contamination sources in Linares city. Groundwater showed a chemical evolution from calcium-bicarbonate type to calciumsodium-sulfate type. The water qualities in the downstream area after Linares are inferior compared to the upstream area before the city. Nitrate concentrations in groundwater increased signicantly after 28 years indicating an important pollutant process in this period of time over the study area. The possible pollution sources could be the agricultural and farm activities, industrial development, landlls leachate, septic tanks and wastewater of municipal and domestic consumption. If the present scenario continues, an aquifer
vila Po rcel (&) H. De Leo n Go mez R. A. Da noma Facultad de Ciencias de la Tierra, Universidad Auto n, Me xico, Carretera a Cerro-Prieto km. 8, de Nuevo Leo Ex-Hacienda de Guadalupe, C.P. 67700 Linares, Mexico e-mail: rene.alberto.davila@gmail.com th C. Schu r Angewandte Geowissenschaften, Institut fu t Darmstadt, Deutschland, Technische Universita Schnittspahnstrae 9, Darmstadt, Germany

vulnerability assessment would be important for the sustainable water management. Keywords Shallow aquifer Urban impact Hydrogeology Hydrochemistry Groundwater management Mexico

Introduction A continuous supply of good water quality is a key factor to reach a good life quality and is important for environmental sustainability and economic growth in urban centers. Natural and man-made factors inuence the quality and quantity of the potable water (e.g. climate, hydrogeological management and pollution process); these variations can be identied over time and space to assess urban development (Shalash and Ghanem 2008). Groundwater is the major source of water for most uses in arid and semi-arid climates. Depending on its usage and consumption, water could be considered as a renewable or non-renewable resource. Approximately one-third of the worlds population use groundwater for drinking and living proposes (Nickson et al. 2005). On the other hand, groundwater quality represents all the processes and reactions that act on the water from the moment it condenses in the atmosphere to the moment it discharges on wells, rivers and lakes. The determination of the suitability of water for a particular use depends on groundwater quality and quantity (Arumugam and Elangovan 2009). In addition, human activities can modify the relative contributions of the natural constituents changing the geochemical evolution by the introduction of pollutants to groundwater resources (Whittemore et al. 1989). The impact level on groundwater quality varies

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widely with the intrinsic pollution vulnerability of the underlying aquifers and with the type and stage of urban development. This is the cause of marked, but essentially diffuse, pollution of groundwater by nitrogen compounds, increasing salinity, elevated dissolved organic carbon concentrations and contamination by fecal pathogens. Urbanization is the most important cause of radical changes in the groundwater recharge process, with a general tendency for volume to increase signicantly and for quality to deteriorate substantially. These changes cannot be measured directly; for this reason, it is very difcult to quantify the deterioration level. Possible sources of these modications to the natural system could be: (a) surface impermeabilization and sewage, (b) irrigation of amenity areas, and (c) introduction of water-service networks through main water-supply and sanitation systems (Foster et al. 1999). Elevated nitrogen concentrations, increased concentrations of chloride (most from excreta), sulphate and borate from detergents and bicarbonate from oxidation of organic matter are frequently observed. The increasing numbers of industries, such as textile mills, tanneries, metal processing, vehicle maintenance, laundry and dry cleaning establishments, printing and photo processing, municipal landll, etc., are located in the urban areas without consideration of the mains sewerage. Most of these industries generate liquid efuents, such as spent lubricants, solvents and disinfectants, which are discharged directly to the ground and can represent a serious long-term threat to groundwater quality (Foster et al. 1999). Although the provision of mains sewage lags considerably behind population growth and water-supply provision, sewage efuent, termed here wastewater, is generated in large volumes by the rapidly developing cities. This wastewater is normally discharged to surface water courses after minimal treatment from where it is used on an uncontrolled basis for agricultural irrigation in the surrounding areas of the urban centers (Foster et al. 1994). For all these reasons, groundwater contamination is always a possibility in shallow aquifers with sub-supercial water table and human presence. These characteristics are present in Linares and Hualahuises region in the northeast of Mexico, where groundwater from these aquifers is the main source for irrigation purposes, industrial use, domestic supply and drinking water. Upstream of Linares City (LC) is the citrus plantation region, the most important activity in the study area and Hualahuises City with many municipal activities that can be pollutant sources to the aquifer, such as: farms, sewage water, oils, hospital waste, automotive service stations, restaurants, small wastewater treatment plant of Hualahuises, leather fabrics and the landll of Hualahuises, are located over this area. On the other hand, in the downstream

area, between LC and Cerro-Prieto Dam (CPD) is the wastewater treatment plant and municipal landll of Linares, citric plantations, stockyards and various human settlements. To analyze the impact of the previous topics and problems, the general objective of this study was dened as follows: evaluate the human impacts on groundwater quality and the hydrochemical evolution in the aquifers over time between upstream and downstream areas of LC to assess the inuence of human activities developed in Linares and its surroundings.

Study area The study area is located in the Planicie Costera del Golfo de Mexico (PCGM) in the northeast region of Mexico, inside Nuevo Leon State (NLS). LC is located in the southern part of NLS 127 km to the southwest by the National Highway No. 85 since Metropolitan-Area of Monterrey (MAM; Fig. 1). To the northeast (*12 km) of LC is positioned the CPD, a drinking water reservoir, an important source of potable water for the MAM (*4.2 Million inhabitants), the most important human center in the northern part of Mexico (INEGI 2010). CPD captures the water of the Pablillo River Basin (PRB); inside its catchment area is LC. Over the last 10 years, industry, agricultural activity and urban growth developed rapidly without any urban development planning. Groundwater supplies more than the 50% of the total drinking water for 70,063 inhabitants in LC (INEGI 2005). Furthermore, the wastewater of the city and the industrial waste water goes downstream directly to the local rivers Camacho and Pablillo, which discharge its waters into the drinking water reservoir CPD (Fig. 1). This situation can easily contaminate the rivers and aquifers affecting the water quality of CPD and groundwater sources for LC inhabitants. The main stream of PRB is Pablillo River, which has Alamos River, Camacho River, Hualahuises River and La Laja River as tributary streams. On the other hand, the average annual rainfall is around 1,035 mm and the average temperature is 22C. Finally, topographic elevations in the study area range from 220 to more than 1,620 m above vila-Po rcel 2011; INEGI 1983b; CNA 2007b). sea level (Da

Materials and methods Geological settings and aquifer framework The study area is part of two important geologic provinces in northeast Mexico: (a) the Sierra Madre Oriental (SMO) which contains the southwestern portion of the basin, and

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Environ Earth Sci (2012) 66:18711880 Fig. 1 Study area

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(b) the Planicie Costera del Golfo de Mexico (PCGM) which includes the northeastern part of the basin area. This research is focused on the PCGM portion of the PRB (Fig. 1). This area was dened due to the following reasons: access to sampling points, topographic relief, human presence, agriculture, livestock and urban activities. Three geological formations were identied, studied and summarized in this study, these formations are, from the youngest formation to oldest formation: (a) Alluvium Conglomerate Formation (ACF) constituted by uvial nchez (1982) terraces and lacustrine sediments; Padilla y Sa assigned a time from Tertiary to Quaternary and this formation has a thickness of *25 m; this material comes from the mountain canyons of the SMO (De Cserna 1956; n-Go mez 1993; Ruiz and Werner 1997; Padilla De Leo nchez 1982); (b) Me ndez Formation (MF), the time y Sa assigned to this unity is Campanian to Maastrichtian

nchez 1982), which has a thickness between (Padilla y Sa 1,500 and 2,800 m consisting of dark gray shale interbedded by olive-green and calcareous shale; and nally, (c) San Felipe Formation (SFF), this unit has an assigned pez-Ramos 1980); it time from Conacian to Santonian (Lo has a range of thickness between 100 and 350 m (Padilla y nchez 1982; De Leo n-Go mez 1993) and is formed by Sa heterogeneous sequence of shale, calcareous shale, silicied limestone, marl and sandstone; this formation is located in a small area on the northern side of CPD (Fig. 2). PRB is a fourth-order basin classication according to Strahler (1957), where a rst-order system is a single stream that has no tributaries; a second-order stream forms at the junction of two or more rst-order streams and so forth (Strahler 1957). The catchment area of PRB has a total area of about 1,735 km2 and the area covered by the

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11 14 7 13 17 5 12 41 23 2 3 9 20 10 19

6 18 21 1622

EXPLANATION
Sampling points Geologic Formations

Description
Alluvial Sediments Conglomerates Mendez Formation

15

San Felipe Formation Alamos River Camacho River Hualahuises River Pablillo River Cerro Prieto Dam

Fig. 2 Aquifer media and sampling points (2009)

perimeter of the study area in this analysis is *820 km2 (northeastern portion of PRB on PCGM). Several investigators have studied the general hydro lez 2000; De geology of the region (De la Garza-Gonza n-Go mez 1989, 1993; Barbar n-Castillo et al. 1988; Leo n-Mancilla 1996; Liza rraga-Mendiola et al. 2004; Galva Lizarraga-Mendiola 2003; Schuster 1999; Moreno-Esparza 2009). However, none of the available literature discussed the hydrochemical evolution of groundwater quality due to anthropogenic presence. The hydrochemical variations in the aquifer over time, groundwater abstraction, land-use development and the human impacts produced during the last 28 years are closely related; for this reason they are important topics to determine the water sustainability in Linares area. Field surveys were conducted to measure the water table in 23 hand-dug wells and pipe wells (Fig. 2); the geographical position was taken with a GPS (Garmin Etrex HCx) and veried with topographic maps from the government database (INEGI 2006). A shallow unconned aquifer which has mainly two hydrologically connected layers was determined within the study area: (a) On the Top, highly permeable and porous aquifer, consisting mainly of gravels and various grades of sand, silt and clay, represented by ACF; and (b) On the Bottom, a fractured and weathered aquifer represented by the presence of MF and SFF. The thickness of the alluvial deposits varies from a few meters to about 25 m in depth and the height of the saturated levels varies according to changes in the consolidation

of the conglomerates and alluvial materials, the variation of aquifer bedrock relief and seasons of the year and the general average of the water table is *10 m in depth (Fig. 3). Groundwater is stored in the fractured and weathered bedrock formations (MF and SFF); the overlying alluvial deposits (ACF) permit the aquifer recharge through vila-Po rcel 2011). The groundwater ow shows its body (Da a SW-NE main direction; and the structural geological data have conrmed this conduct, the local groundwater pathways end at the CPD as the surface ow of the basin. Hydraulic conductivity (K) was measured on eld by pumping tests, K varies from 2.28 9 10-6 to 3.4 9 10-4 m/s lez 2000), which lies in the range (De la Garza-Gonza expected for similar aquifer environments (Domenico and Schwartz 1998; Fetter 2001). The discharge of the aquifer takes place in CPD and through pumping in LC and its neighboring areas. Linares has semi-arid climatologic conditions, and the recharge to shallow alluvial aquifers usually occurs from inltration from surface (MorenoEsparza 2009). The principal process of recharge is the inltration from the surface over the aquifer in the PCGM area. The shallow water table and coarse alluvial sediments increase the probability of direct recharge into the alluvial aquifer. The amount of recharge is dependent on the frequency of rainfall, which is characterized by large temporal and spatial variations. The average annual rainfall in the study area is 1,035 mm (25 years of monthly register) and a range from *18 to 35% of the annual precipitation converts vila-Po rcel 2011). to recharge (CNA 2007a, b; Da

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Environ Earth Sci (2012) 66:18711880 Fig. 3 Groundwater levels and main ow direction
400 380 420 430 330 340 360 410 390 420 350 330 300 350 310 330 320 310 300

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450

EXPLANATION
430 440

Piezometric lines Flow direction Cerro Prieto Dam

2.5

10

15

20

Kilometers

Sampling and methodology A total of 23 groundwater samples were collected from hand-dug wells and pipe wells during March 2009; these sampling points are located in the surroundings of LC and HC. The multi-parameter measuring equipment, WTW340, was used for the onsite analysis of electrical conductivity (EC), pH, redox potential (Eh) and temperature (T). The water samples were ltered through 0.45 lm glass-ber papers; they were stored in pre-cleaned bottles of 1-1 polyethylene and refrigerated at 4C. In the laboratory, alkalinity was measured using the titration method; this parameter was reported as mg/l of CaCO3, which is then multiplied by a standardized factor, the ratio of the equivalent weights of bicarbonate to calcium carbonate, to calculate bicarbonate concentration. The measurement of ions was performed by Dionex ICS-90 IC (Ion Chromatography). The nal concentrations of major cations are included in the hydrochemical database: Sodium (Na?), Potassium (K?), Calcium (Ca2?), Magnesium (Mg2?), as well as, the major anions: Bicarbonate (HCO3-), Chloride (Cl-), Nitrate (NO3-) and Sulfate (SO42-) which were determined with Dionex ICS-120 at the Hydrochemical Laboratory in the Institute of Applied Geosciences at the Technical University Darmstadt (Germany). Table 1 shows the results of the laboratory analyses carried out in 2009. stica, Geograf a e The Instituto Nacional de Estad Informatica (INEGI 1983a) during November of 1981 made groundwater sampling of many wells and hand gica de Aguas dug wells to elaborate the Carta Hidrolo neas (G1411) 1:250.000; 25 wells of this sampling Subterra season are within of PRB perimeter. These water samples were analyzed in a laboratory and its name is not indicated.

Table 2 illustrates the results of the water quality in 1981. All these information are available on the back of the map mentioned above.

Hydrochemical results The hydrogeochemical analysis results and the comparison of groundwater quality between 1981 and 2009 are summarized in Table 3. In this study, the 2009 database represents the current conditions and the 1981 database represents the previous water quality. The groundwater temperature average has a variation from 21.53C upstream of LC to 23.58C downstream area; this means at least a 2C discrepancy. In general, these values are close to the atmospheric temperature, and they may be linked to the shallow depth of the groundwater table (Moussa et al. 2009). The higher values of EC are associated with wells away from the rivers indicating probably a longer residence time; a couple of them are located near industrial areas, and one of them is placed in the downstream area of the LC near the CPD, indicating less interaction with the alluvial aquifer or more time-residence in the fractured aquifer. Finally, a linear correlation exists between EC and total dissolved solids (TDS) for the analyzed samples with a mathematical relation EC (lS/cm) = 194.09 ? 1.1824 9 TDS (mg/l). The local groundwater has pH values that are in the usual range of natural groundwater (Hem 1985). However, the pH average values in the upstream area of 7.83 in 1981 and 7.33 in 2009 are similar to downstream values of 7.89 in 1981 and 7.05 in 2009 in both cases. During 1981, the pH was more alkaline and does not reveal great contamination either by domestic and industrial

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Table 1 Chemistry of groundwater in 2009; values are expressed in mg/l, except indicated otherwise Sample 200901 200902 200903 200904 200905 200906 200907 200908 200909 200910 200911 200912 200913 200914 200915 200916 200917 200918 200919 200920 200921 200922 200923 TDS 185.0 815.0 677.6 2187.4 1423.0 6817.2 621.0 270.6 870.2 512.0 349.0 854.2 650.6 286.8 340.2 782.4 1051.8 900.6 720.4 955 505.8 545.4 670.4 pH 7.5 8.1 7 6.7 6.8 6.8 6.9 7.5 7.3 7.3 7.9 7.7 7.5 7.5 6.9 6.7 6.8 7 6.6 6.7 7.0 7.0 6.9 T (C) 21.7 22.5 23.5 22.8 22.9 21.9 23.7 19.7 25.3 20.1 21.5 21.6 22.4 20.3 23.3 25.3 23.0 25.1 25.3 20.6 25.4 24.2 25.8 EC (lS/cm) 1,603.0 1,105.0 968.0 2,790.0 1,954.0 8,240.0 1,002.0 482.0 1,188.0 763.0 542.0 1,163.0 932.0 474.0 658.0 1,194.0 1,540.0 1,052.0 1,256.0 1,150.0 836.0 859.0 964.0 Eh (mV) 227.0 234.0 288.0 222.0 247.0 278.0 253.0 307.0 220.0 231.0 311.0 263.0 273.0 312.0 314.0 222.0 247.0 215.0 254.0 148.0 231.0 227.0 255.0 Ca2? 225.7 157.8 181.5 375.3 270.9 542.8 149.7 84.3 208.4 131.2 90.2 192.4 148.8 90.4 125.3 201.1 243.6 209.6 160.0 221.2 159.5 145.7 189.8 Mg2? 24.5 21.0 9.7 36.8 30.3 143.8 14.3 7.4 13.3 7.6 6.7 19.6 13.9 6.0 6.6 11.7 23.6 17.4 23.4 15.1 8.5 8.5 9.7 Na? 103.3 41.9 27.5 176.0 126.9 271.6 67.3 12.9 43.6 19.4 19.6 41.7 32.4 7.9 14.5 49.8 75.9 43.4 93.0 32.4 22.3 22.4 24.6 K? 23.2 3.0 3.2 2.8 1.2 17.1 1.3 1.0 2.2 2.3 0.6 0.9 1.3 0.6 1.2 7.3 2.9 4.3 1.7 0.6 1.6 1.1 1.2 HCO3291.7 63.8 258.3 315.0 380.7 326.2 334.0 252.1 252.8 200.4 219.3 197.3 218.2 243.2 323.9 359.8 347.3 236.2 421.3 324.5 238.0 226.6 288.6 Cl216.8 135.2 24.5 521.1 128.6 708.2 64.1 3.7 80.4 18.0 11.0 54.7 44.4 3.1 5.7 57.7 157.6 54.3 89.0 26.8 22.2 18.7 23.6 SO42165.3 343.2 240.2 307.7 349.7 201.4 94.9 17.6 267.4 163.9 40.1 351.3 180.2 26.2 26.7 169.7 171.6 345.2 65.7 249.4 183.2 167.1 215.2 NO353.3 0.5 14.2 73.2 170.5 1287.8 28.1 0.0 33.7 6.2 19.4 24.9 24.6 1.5 11.1 40.5 61.8 30.8 50.3 7.3 17.3 9.8 11.7

wastewater. High calcium concentration may be due to contamination by agricultural and industrial efuents and concentrations of bicarbonate more than 200 mg/l are common in groundwater (Matthes 1982). One possible source is organic matter in water which oxidize to produce carbon dioxide. This process enriches Ca, Mg, and bicarbonates. High chloride and sodium concentration can result from dissolution of soil and rock minerals or percolation of septic systems. Based on the local data of geological formations and hydrochemical characteristics, the chloride concentration may result in percolation of septic water and sewage waste water since chloride is an indicator of septic system pollution (Alhajjar et al. 1990). High nitrate concentration in groundwater is a strong indication of direct contamination to the aquifer. Nitrate could increase its values over the time mainly in the downstream area due to the groundwater ow. The groundwater quality represents a natural chemical evolution through the aquifers and some inputs of human activity. The cation composition of the water goes from calcium to sodium presence; the anion compositions are bicarbonate and sulfate predominates in the area, this indicates that water within the alluvial aquifer is of alkaline type with prevailing sulfate and chloride (Al-Shaibani 2008). The cation composition probably varies as a result

of the rocks chemistry, which comes into contact or deposition of contaminants through the ow course. The information generated by INEGI (1981) for groundwater quality of both upstream and downstream of LC in the aquifer represents a historical database and is possible to use because the chemical balance of cations and anions is good in terms of equivalent weights (average error % *0.1). The histogram in Fig. 4 shows the average concentrations of groundwater constituents for both upstream and downstream of LC and HC in 1981 and 2009. In advance, the groundwater type of the upstream area has a good quality; mostly calcium-bicarbonate predominates over 28 years. There is a clear increase in Na ? K and 2 SO4 concentration in the groundwater of the downstream area from SW to NE of LC in the direction of CPD. Sodium adsorption ratio (SAR) and salinity are two main criteria to evaluate irrigation water quality. The Wilcox diagram is used to classify irrigation waters (Hounslow 1995); based on this classication, groundwater of the downstream area in 1981 has medium salinity hazard and low sodium hazard. For 2009, over the same area, groundwater has high salinity hazard and low sodium hazard. The groundwater of the upstream area has better quality for irrigation proposes in both years (1981 and 2009); a medium salinity hazard and low sodium hazard

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Environ Earth Sci (2012) 66:18711880 Table 2 Chemistry of groundwater in 1981; values are expressed in mg/l, except indicated otherwise Sample 198101 198102 198103 198104 198105 198106 198107 198108 198109 198110 198111 198112 198113 198114 198115 198116 198117 198118 198119 198120 198121 198122 198123 198124 198125 TDS 408.0 492.0 482.0 318.0 939.0 495.0 504.0 428.0 501.0 669.0 492.0 703.0 699.0 378.0 472.0 525.0 373.0 2,987.0 587.0 866.0 342.0 980.0 654.0 563.0 601.0 pH 7.9 8.3 8.1 7.7 8.0 8.1 8.1 7.6 8.1 8.1 8.1 7.7 7.6 8.0 7.6 7.9 7.6 7.6 7.9 7.4 7.8 7.8 8.1 7.6 7.5 EC (lS/cm) 560.0 700.0 590.0 380.0 1,240.0 720.0 810.0 550.0 670.0 870.0 560.0 920.0 1,210.0 580.0 620.0 660.0 560.0 4,900.0 720.0 1,220.0 460.0 1,510.0 830.0 670.0 810.0 Ca2? 86.0 93.0 72.0 37.0 114.0 102.0 102.0 76.0 100.0 136.0 78.0 101.0 117.0 40.0 70.0 62.0 48.0 420.0 102.0 192.0 54.0 119.0 117.0 45.0 62.0 Mg2? 10.1 15.8 16.6 20.0 55.4 13.7 16.4 12.5 14.9 20.6 18.5 31.7 27.5 19.3 23.8 19.2 17.2 157.2 22.1 18.6 13.4 51.0 25.9 30.0 19.8 Na? 16.8 17.0 30.4 18.2 62.3 19.5 20.0 19.5 20.9 23.5 29.0 58.4 49.0 23.9 23.9 59.8 41.4 386.9 24.4 34.3 20.0 106.0 32.0 63.5 78.4 K? 0.4 0.4 1.2 0.0 6.6 0.4 0.4 0.0 0.4 0.4 0.4 0.4 0.4 4.3 0.8 0.4 0.4 0.8 0.4 0.4 0.4 0.4 0.8 0.4 0.4 HCO3122.0 140.3 256.0 176.9 146.4 146.4 146.4 262.3 146.4 176.9 213.5 213.5 244.0 286.7 189.1 213.5 97.6 189.1 268.4 231.8 140.3 213.5 134.2 347.7 298.9 Cl3.5 17.8 10.6 3.5 198.8 35.5 28.4 14.2 28.4 60.3 14.2 95.8 53.2 3.5 28.4 31.9 35.5 1,164.4 21.3 87.7 7.1 131.3 28.4 42.6 28.4 SO42166.6 206.4 83.0 62.4 350.1 177.1 187.1 41.3 187.7 250.1 135.4 187.7 187.7 0.0 135.4 135.4 124.8 667.7 145.9 281.3 104.2 354.7 313.0 31.2 104.2

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NO32.5 1.2 12.4 0.0 5.0 0.0 2.5 2.5 2.5 1.2 2.5 2.5 2.5 0.0 1.2 2.5 2.5 1.2 2.5 7.4 2.5 3.7 2.5 2.5 2.5

Table 3 Comparison of the chemical analyses results for groundwater samples upstream and downstream of LC between 1981 and 2009; average values expressed in mg/l, except indicated otherwise

Upstream groundwater 1981 TDS EC (lS/cm) pH T (C) Eh (mV) Calcium Magnesium Sodium Potassium Chloride Sulfate Nitrate Bicarbonate Carbonate 75.50 21.48 36.41 1.04 35.88 132.16 2.63 209.08 2.33 516.50 695.00 7.83 2009 743 1,028.71 7.33 21.53 264.00 163.50 14.23 43.59 1.39 100.92 144.41 16.16 248.83 % Difference 30.52 32.44 -6.87 100.00 100.00 53.82 -50.89 16.47 25.05 64.45 8.48 83.74 15.97

Downstream groundwater 1981 1,023.00 1,544.29 7.89 2009 1,168.01 1,594.63 7.05 23.58 245.69 169.43 43.51 89.09 0.51 218.41 320.31 3.00 176.90 1.71 210.05 23.74 66.56 4.55 110.18 208.25 116.58 286.09 % Difference 12.42 3.16 -11.92 100.00 100.00 19.34 -83.30 -33.85 88.70 -98.34 -53.81 97.43 38.17

are dominant (Table 4; Fig. 5). It must be remembered that there is almost 30 years between both analyses and differences in collection procedures, handling techniques,

analysis equipment and interpretation methods do not signicantly affect the comparative analysis of groundwater chemical conditions.

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1878 Fig. 4 Comparison between 1981 and 2009 of anions and cations contents in groundwater

Environ Earth Sci (2012) 66:18711880

Table 4 Matrix classication of irrigation water quality, signicance and coverage for the samples in the study area

Classication C2S1 C3S1 C4S1 C4S2 Coverage % Coverage

1981 Downstream 1 5 0 1 7 14.58

1981 Upstream 14 4 0 0 18 37.50

2009 Downstream 0 15 0 1 16 33.34

2009 Upstream 4 2 1 0 7 14.58

Signicance 19 26 1 2 48

% Signicance 54.17 39.59 2.08 4.16 100.00

Discussion Geochemical analyses both upstream and downstream of the city of Linares are listed in Table 3. It is possible to observe a natural mineralization from SW with initial domain of calcium to bicarbonate as major ions and a nal domain in the NE of calcium and sodium ions. The groundwater of the upstream area is of better quality in 2009 than in 1981. In relation to this, two important observations can be made: (a) the aquifer water has been diluted by a direct recharge of rainfall water and (b) in 1981 the samples are less separated, in contrast with the samples of 2009, that means a better quality of local fresh water that might be responsible for the natural recharge. The groundwater of the downstream area of 2009 has almost the same general groundwater quality of 28 years ago. However, the distribution of sampling points of 1981 has a large distribution that indicates a progressive change of groundwater quality due to the dilution of magnesium and calcium, contained inside the aquifer rocks lithology. The relative concentrations of the groundwater samples in 2009 represent a similar water quality compared with the

situation of 1981, due to the general mineralization. The main change could be due to the distribution of pollutants as a product of the large areas of citrus plantations, urban human activities and industrial development. The spatial distribution of groundwater quality is variable; in the upstream part of the study area of LC and close to SMO represents the hydrogeochemical background condition (SW), considered as the zone of natural water quality or recharge zone in comparison with the downstream area over the eastern region of LC in the PCGM. The upstream area around Hualahuises city can be considered the most important pollution source compared with the downstream areas of this urban center. Parallelly, the industrial and human activity of LC could generate important pollution due to sewer systems and wastewaters. Nitrate is probably the most commonly used indicator in groundwater pollution by septic systems or the agricultural land-use patterns (Moussa et al. 2009). The area around LC and HC is heavily cultivated and irrigated; sewerage leaks are common and cattle barns exist inside the study area. Solid wastes generated by the population of Linares were deposited in the municipal landll during 21 years

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Environ Earth Sci (2012) 66:18711880 Fig. 5 Groundwater quality for irrigation proposes

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(19842005). Groundwater quality was analyzed from several hydraulic wells located near the landll, as well as in areas where possible pollution sources exist (barite deposits, pig farms, septic tanks and latrines). Taking several norms as a basis, the results showed contamination by total and suspended solids, total and fecal coliforms, nitrate and DNAPLs (dense non-aqueous phase liquids) such as mercury, barium and arsenic. The migration of contaminants is inuenced by the local ow system of groundwater and it was determined that the most vulnerable zones are located mainly downward of the municipal landll with the same direction that groundwater ows from SW to NE. All the pathways of the regional and local rragagroundwater ow system nish at the CPD (Liza vila-Po rcel 2011). Mendiola et al. 2004; Da

Conclusions A hydrogeological and hydrochemical study was conducted on a shallow alluvial aquifer over Linares region in northeast Mexico. The aquifer hydrochemistry was compared between the upstream area and downstream area with reference to LC for two different situations over 28 years of difference. According to the water table of the study area, the ow goes from SW to NE direction to the CerroPrieto Dam (drinking water reservoir). Many changes in chemical composition were expected as a result of the evolution of water chemistry along the regional ow

pathways. Most of the samples in the downstream area have generally higher concentrations of chemical constituents in comparison with the samples in the upstream area. In both years (1981 and 2009) the same mineralization process is present; the main differences are the elevated values of some constituents, which can be considered as indicators of contamination (i.e. nitrate, chloride, sulphate, borate and high TDS). The source of contamination can be attributed to incidental or induced inltration of sewage water, wastewater treatment efuent, leachate from cattle farm wastes and municipal landlls, leakage from sanitary sewers, septic deposits and surface contamination due to agricultural customs and practices. In the downstream area, groundwater quality is changing due to increased concentration of calcium and bicarbonate by the natural mineralization process. Nitrate concentration has experienced a signicant increment from 1981 to 2009 denoting general and extended pollutant process over the study area. The nitrate concentrations exceed the recommended values of the World Health Organization. If the present situation continues, the future scenario will be very conictive; for this reason, it would be useful to develop an Intrinsic Aquifer Vulnerability Assessment and identify pollutant risky areas in the region of LC and inside the PRB.
Acknowledgments This study was partially supported by the Uni noma de Nuevo Leon, Me xico, PAICyT project CT versidad Auto 1584-07 (2008). Thanks to the sandwich doctoral program supported by the Deutscher Akademischer Austausch Dienst/DAAD, Facultad xico. The authors would also like de Ciencias de la Tierra/UANL, Me

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1880 to thank the associate editor and the anonymous reviewers for their valuable comments.

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