Hydrogeochemical features of groundwater resources in Tabriz plain, northwest of Iran
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Abstract
The present study seeks to evaluate the hydrogeochemistry of Tabriz plain in NW Iran, through major ion chemistry and their spatial variations. In order to accomplish these, groundwater sampling from 30 shallow and deep wells in the plain were carried out in July 2012. The water samples were analyzed for various physicochemical parameters such as pH, EC, Na+, Ca2+, K+, Mg2+, Cl−, CO3 2−, HCO3 −, SO4 2− and NO3 −. Chadha’s diagram demonstrates that most of the groundwaters belonged to the Na–Cl and mixed Ca–Mg–Cl hydrochemical facies. The concentrations of some major ions in groundwater are above the permissible limit for drinking and domestic purposes except for a few locations. The results of saturation index computation show that dissolution of gypsum, anhydrite, halite and silicate minerals occurs frequently across the study area, whereas the groundwater is supersaturated with regard to calcite and dolomite. Cross-plots show that weathering and dissolution of different rocks and minerals, ion exchange, reverse ion exchange and anthropogenic activities, especially agricultural activities, are effective in hydrogeochemistry of the study area.
Keywords
Groundwater Hydrogeochemistry Saturation index Tabriz plain IranIntroduction
Groundwater resources are important for the socio-economic development, especially in arid and semi-arid regions (Tlili-Zrelli et al. 2012). Water quality refers to the natural, physical and chemical state of the water as well as any alteration that might have been caused by anthropogenic activity (Venkateswaran et al. 2011; Jafar Ahamed et al. 2013). The groundwater quality, which is normally controlled by variable physicochemical characteristics, is the outcome of all those processes and reactions that act on water from the moment it condenses in the atmosphere till the time it is exploited by a well (Arumugam and Elangovan 2009).
Hydrogeochemical evaluation of groundwater systems is usually based on the availability of a large amount of information concerning groundwater chemistry. Many factors such as climate, soil type, mineralogy of the rock types forming catchments and aquifers, area topography, overlying land uses, source of recharge water, atmospheric inputs, etc., may affect groundwater chemistry (Reghunath et al. 2002; Singh et al. 2004; Tziritis et al., 2016). In addition to these factors, the interaction between surface and groundwaters as well as the groundwater mixing of different origins and characteristics may also have a significant impact on hydrogeochemistry (Reghunath et al. 2002). Groundwater contains many chemical constituents, both natural and man-made. Generally, major ion studies are used to determine hydrochemical facies of waters and the spatial variability of these ions can give insight into aquifer heterogeneity and connectivity as well as into the ongoing hydrogeochemical process of the groundwater system (Belkhiri et al. 2012). Major ion chemistry, in particular molar ion ratios, is useful in assessing the sources of solutes and characterizing hydrogeochemical origin and evolution in aquifers (e.g., Cartwright et al. 2004; Currell and Carthwright 2011; Voutsis et al. 2015). The geological history of the aquifers can be obtained from investigation of the groundwater chemistry (Aghazadeh and Asghari Moghaddam 2010; Das and Nag 2015).
Hydrogeochemical assessment of the water systems is of significant importance; especially, in populated regions which depend on groundwater. Tabriz district is one of the most densely populated, active intensively farming and industrial area in the northwest of Iran. Due to scarcity of suitable surface waters, groundwater is the only available water resource which supplies drinking, irrigation and industrial demands of the area. A few studies have been carried out on the hydrogeology and hydrogeochemistry of the area (CITRA-SOGREAH-CCG-HYDRA 1965; ELC-ELECTRO Consult 1969; Asghri Moghaddam 1991; Asghri Moghaddam and Allaf Najib 2006). Barzegar et al. (2015) reported the occurrence of heavy metals and metalloids such as Fe, Cr, Mn, Al and As in the Tabriz plain aquifer. They concluded that the arsenic concentrations in the unconfined aquifer and in the recharge areas of the plain boundary (with an average of 25.8 µg/L) were lower, than those in the confined aquifer and the deeper wells, which had an average value of 122.5 µg L−1. The arsenic occurrence in groundwater resources of the area was attributed to the geological formations such as alluvial tuffs of Sahand Mountain; its concentration is highly dependent on the redox conditions within the aquifer systems and, subsequently on the hydrogeological regime, residence time of water and aquifer depth.
With the above background, the main objectives of this study are: (1) to assess the major ion chemistry of groundwater; (2) to identify the hydrogeochemical processes affecting the groundwater chemistry. The development of groundwater resources in the region is a sensitive issue in environmental and socio-economic terms. Therefore, sustainable management is required to avoid water quality degradation, which depends on detailed knowledge of the groundwater chemistry.
Materials and methods
Study area
Location map of the study area and its drainages
Monthly averages of precipitation, temperature and humidity
Agriculture and industry are the main human activities in the study area. Industrial activities are relatively intensive in the west of the Tabriz city. Fertilizers that contain nutrients such as nitrogen are used excessively to increase production in the agricultural lands. Numerous factories, including petrochemical, leather tanning, metal smelting and food processing are located in the study area. A large volume of waste water is released from these factories which enter into the Aji-Chay River.
Geology and hydrogeology
Geological map of the study area
The Plio-Pleistocene volcanic tuffs have an extended exposure and overlie the Pliocene beds to the south of the Tabriz plain around the core of the Sahand volcano. The formation consists of red and green andesite tuff admixed with large quantities of blocks, boulders, gravel and sand of volcanic and alluvial origin with thickness of up to 500 meters and it has good quality groundwater resources (Barzegar et al. 2015, 2016b).
Simplified stratigraphic sequence in the study area (after ELC–ELECTRO Consult 1969)
The Aji-Chay River, most important river in the area, enters to the plain from its northwest boundary, and flows along the central part of the plain towards the west, and at the end of the plain eventually discharges to the Urmia Lake (Barzegar et al. 2016d, 2017). The Mehran-Rood River passes inside the Tabriz city and then joins the Aji-Chay River at the western end of the city. The Gomanab-Chay and Sinekh-Chay Rivers join to the Aji-Chay River from right bank side and the Sard-Rood and Onsor-Rood Rivers from left bank side (Fig. 1). These rivers form alluvial fans at the entrance of the plain (Barzegar and Asghari Moghaddam 2016).
A schematic position of the aquifer types and location of the sampling points in the study area
Schematic cross sections in the study area along the A–A’ and B’–B lines (positions marked in Fig. 3)
The hydraulic parameters of the aquifers are widely variable due to the lithological and geometric variability of the deposits. Pumping test analyses showed that the values of transmissivity for the confined aquifer ranged from 820 to 2174 m/d, whilst an average transmissivity of the order of 3500 m/d was obtained from the pumping test analyses of the unconfined aquifer (Barzegar et al. 2016c).
Groundwater sampling and chemical analysis
Descriptive statistics of EC, pH, analyzed ions and some computed minerals saturation indices for the groundwater samples
Unit | Minimum | Median | Mean | Maximum | Variance | Std. deviation | |
---|---|---|---|---|---|---|---|
EC | µS cm−1 | 693.00 | 3400.00 | 4300.00 | 12,500.00 | 8.6 × 106 | 2940.00 |
pH | – | 7.50 | 7.90 | 7.90 | 8.40 | 0.05 | 0.23 |
Ca2+ | meq L−1 | 1.95 | 10.04 | 10.26 | 23.00 | 36.78 | 6.06 |
Mg2+ | meq L−1 | 0.96 | 6.62 | 7.89 | 24.00 | 24.31 | 4.93 |
Na+ | meq L−1 | 1.60 | 16.62 | 27.8 | 93.91 | 615.66 | 24.81 |
K+ | meq L−1 | 0.35 | 0.95 | 1.30 | 3.80 | 0.72 | 0.84 |
HCO3 − | meq L−1 | 3.83 | 5.75 | 6.15 | 10.87 | 3.36 | 1.83 |
CO3 2− | meq L−1 | 0.00 | 0.00 | 0.18 | 0.88 | 0.084 | 0.28 |
Cl− | meq L−1 | 1.40 | 19.40 | 31.70 | 113.00 | 876.00 | 29.59 |
SO4 2− | meq L−1 | 1.29 | 7.18 | 8.12 | 17.68 | 24.19 | 4.91 |
NO3 − | meq L−1 | 0.01 | 0.68 | 0.89 | 3.93 | 95.00 | 0.97 |
SICalcite | – | 0.10 | 0.98 | 0.91 | 1.25 | 0.10 | 0.32 |
SIDolomite | – | 1.13 | 2.21 | 2.09 | 2.91 | 0.16 | 0.41 |
SIGypsum | – | –2.39 | –0.109 | –1.04 | 0.86 | 0.42 | 0.65 |
SIAnhydrite | – | –2.61 | –1.30 | –1.35 | –0.70 | 0.17 | 0.42 |
SIHalite | – | –7.32 | –5.25 | –5.15 | –3.13 | 0.71 | 0.84 |
Results and discussion
Hydrochemical facies
Chadha’s diagram showing chemical characteristic of groundwater in the Tabriz plain aquifer
Spatial variability of groundwater quality parameters
Spatial distribution of a EC, b pH, c Ca2+, d Mg2+, e Na+, f K+, g HCO3 −, h SO4 2−, i Cl−, j NO3 − concentration in the study area
The distribution map of pH values (Fig. 8b) shows that pH is high in the eastern part of the study area due to high bicarbonate levels in groundwater, while pH levels are decreased towards the central parts due to low levels of bicarbonate and high salinity. As well as, groundwater pH increases with water residual time because the interaction of water–rock will consume H+ (Hinkle and Polette 1999). Therefore, pH is increased in the central parts of plain due to low hydraulic gradient and high water residual time.
The calcium content of the samples varies between 39 and 460 mg L−1. According to World Health Organization (WHO) (2011) standards, its permissible range in drinking water is 75 mg L−1. Calcium in the groundwater can originate from Miocene and Pliocene formations, e.g. limestone, sandstone, conglomerate, gypsum in the study area. Concentration of calcium against sodium is low, revealing a lack of soluble calcium minerals, as calcium of groundwater is replaced by sodium through ion exchange reaction (Sharma and Rao 1997).
Spatial distribution of bicarbonate ion is shown in Fig. 8g. Bicarbonate concentrations range between 234.1 and 663.1 mg L−1. Elevated Ca concentrations may be attributed to dissolution of limestones, Ca-rich feldspars, and potentially due to biodegradation or organic matter in upper soil horizons.
Sulfate concentrations vary between 62.2 and 847.6 mg L−1 (Fig. 8h). Sulfate concentration greater than 50 mg L−1 causes a bitter taste in water and in higher concentration of 400 mg L−1 with calcium and magnesium can cause frailty in the body (Shankar et al. 2008). Anomalies of sulfate spatial shows compliance with calcium and magnesium distribution maps which indicates these ions originate from dissolution of Miocene and Pliocene formations which contain gypsum and anhydrite. The concentration of sulfate shows a high anomaly in Tabriz city which is affected by contamination from municipal and industrial wastewater. Also, irrigation water return flow can be another source of the SO4 2− in the groundwater of the study area.
Chloride concentrations range between 49.7 and 2041.2 mg L−1 in the groundwater of the aquifers (Fig. 8i). According to World Health Organization (WHO) (2011), concentration of chloride should not exceed 250 mg L−1. The origin of chloride in groundwater of the study area can originate from evaporative deposits of the Miocene formations, contamination from municipal waste and urban waste and irrigation water return flow. This statement can be confirmed with moderate-to-high correlations between Cl− and Na+ (r = 0.965), Cl− and K+ (r = 0.843), Cl− and SO4 2− (r = 0.617). The chloride increase in the plain groundwater is justified by evaporative conditions due to shallow water level, fine-grained sediments and low hydraulic gradient and thus more groundwater residual time and more dissolution.
Nitrate concentrations vary between 4 and 243.7 mg L−1 with an average concentration of 55.6 mg L−1 (Fig. 8j). Many parameters such as the amount of fertilizer used, surface water quality, land use type, depth of groundwater level, land drainage by the river and sediment type have resulted in variations of nitrate concentrations in different parts of the plain (Barzegar 2014). The lowest nitrate concentration is obtained from the northwest of the plain (sample 16) because of low agricultural activity, confined aquifers in these areas and fine-grained sediments in comparison with other parts of the area. The highest nitrate concentration (sample 29) is in the west of Tabriz city, which is attributed to urban and domestic sewages and dense farming in this area (Barzegar 2014). Nitrate concentration is much higher in the southern part of Aji-Chay River; it would be due to intensive agricultural activity, industrial concentration, type of aquifer and shallow groundwater. The presence of high nitrate concentration in the drinking water increases the incidence of gastric cancer and other potential hazards to infants and pregnant women (Nagireddi Srinivasa Rao 2006).
DRASTIC vulnerability map of the study area with NO3 − concentrations
Identification of the hydrochemical processes
Plots of major ions versus TDS
Plots of a (Ca2+ + SO4 2−) versus SI of gypsum, b (Ca2+ + SO4 2−) versus SI of anhydrite and c (Na+ + Cl−) versus SI of halite
Plots of a SO4 2− versus Ca2+, b Na+ versus Ca2+ + Mg2+, c EC versus Na+/Cl− and d TC versus Na+ + K+
The plot of Na+/Cl− versus EC was used to characterize the impact of the evaporation on the groundwater chemistry. This plot would give a horizontal line, which would then be an effective indicator of the concentration by evaporation, evapotranspiration and halite dissolution. Theoretically, the Na+/Cl− ratio approximately equal to one is attributed to halite dissolution, whereas a ratio greater than one is typically indicative for Na+ release due to silicate weathering (Meybeck 1987). Generally the molar ratio of Na+/Cl− for groundwater samples ranges from 0.38 to 2.1 (Fig. 12b). Most of the samples have Na+/Cl− molar ratio below one, indicating that halite dissolution was the major process. Scatter plot of EC versus Na+/Cl− shows an inclined trend line, which indicates that evaporation may not be the major geochemical process controlling the chemistry of the groundwater. As well as, halite dissolution indicates by the well-defined relationship in the correlation of the negative saturation indices versus the sum of ions resulting from the NaCl dissolution (Fig. 11c).
The impact of silicate weathering on groundwater system can be found by plot of Na+ + K+ versus total cations (TC). As shown in Fig. 11d, most of the data points are plotted above the Na+ + K+ = 0.5 TC. This indicates the involvement of silicate weathering in the groundwater system, which contributes Na+ and K+ to the groundwater (Stallard and Edmond 1983; Rajmohan and Elango 2004; Senthilkumar and Elango 2013).
Plot of TDS values versus (NO3 − + Cl−)/HCO3 − molar ratios
Plots of a log TDS versus Na+/(Na+ + Ca2+) and b log TDS versus Cl−/(Cl− +HCO3 −) (after Gibbs 1970)
Conclusions
Electrical conductivity (EC) values of the groundwater are highly variable. The elevated EC values should be chiefly attributed to irrigation water return flow. However, additional causes such as the induced evaporation due to low depth of water table, the hydraulic connection with the Aji-Chay River and, the dissolution of evaporitic formations act as supplementary sources of salinization and contribute the overall outcome. Mixed Ca–Mg–Cl and Na–Cl type of groundwater is predominant in the study area. The concentrations of some major ions in groundwater are above the permissible limit for drinking and domestic purpose except for a few locations. Na+ and Cl− are strongly correlated with TDS with an R 2 of 0.9374 and 0.9739, respectively, which indicates that these ions are the most effective in the mineralization and salinization of the groundwater of the study area. Scatter plots show that rock–water interaction, evaporation, cation exchange and anthropogenic activities are predominant processes that take place in the aquifer. A strong correlation with R 2 = 0.8603 between TDS values and (NO3 − + Cl−)/HCO3 − molar ratios indicates the impact of human activities on groundwater chemistry. The results of saturation index (SI) computation and different scatter plots show that dissolution of gypsum, anhydrite, halite and silicate minerals occurred frequently across the study area, while groundwater is supersaturated with respect to calcite and dolomite; therefore, these minerals precipitate in the groundwater.
Notes
Acknowledgements
The authors are thankful to Mr. Masoud Orouji and Mrs. Naeimeh Kazemian for their help in analyzing of the water samples and Mr. Mortaza Najib for his kind help in the collection of some data.
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