International Journal of Civil Engineering and Technology (IJCIET) Volume 10, Issue 04, April 2019, pp. 1538-1547, Article ID: IJCIET_10_04_160 Available online at http://www.iaeme.com/ijciet/issues.asp?JType=IJCIET&VType=10&IType=04 ISSN Print: 0976-6308 and ISSN Online: 0976-6316 © IAEME Publication Scopus Indexed GEOCHEMISTRY, QUALITY APPRAISAL OF GROUNDWATER AND HYDROGEOCHEMICAL PROCESS IN MIDDLE OUERRHA, TAOUNATE, RIF – MOROCCO Ahmed El Bakouri* Team of Waters, Wastewaters, Laboratory of Environment and Quality, Faculty of Sciences, Ibn Tofail University, Kenitra, Morocco Khadija El Kharrim Team of Waters, Wastewaters, Laboratory of Environment and Quality, Faculty of Sciences, Ibn Tofail University, Kenitra, Morocco Mohamed Tayebi Team of Valorisation of Georesources and Territorial Planning, Laboratory of Geosciences and Environment, Faculty of Sciences, Ibn Tofail University, Kenitra, Morocco Driss Belghyti Team of Waters, Wastewaters, Laboratory of Environment and Quality, Faculty of Sciences, Ibn Tofail University, Kenitra, Morocco *Corresponding Author ABSTRACT A hydrogeochemical study was conducted in the Middle Ouerrha, Taounate, Morocco, to identify the mechanisms responsible for the chemical compositions of the shallow groundwater and to document water quality. Different physicochemical parameters are determined, and correlation were used to reveal the hydrogeochemical characteristics of the shallow groundwater, and the potential water-rock interactions. Groundwater samples were collected from a natural source and two wells. Unfortunately, the groundwater of Taounate district have know the problem of salinity, which threatens their quality. In the Hammam source were characterized by high levels of salinity. The temperature, pH, electrical conductivity, salinity, Ca, Mg, Cl, SO4, K, NO3, Na and HCO3 were determined. The predominant mechanism controlling groundwater chemistry proved to be the dissolution of carbonates, salt red marls and gypsum. The purpose of this study was to identify salinity water sources and quantitatively analyze their composition using comprehensive hydrogeochemical \http://www.iaeme.com/IJCIET/index.asp 1538 editor@iaeme.com Ahmed El Bakouri, Khadija El Kharrim, Mohamed Tayebi and Driss Belghyti determinations. This approach facilitates important decision making for water salinity disaster control, and quickly and accurately solves the fuzzy and uncertain characteristics of water quality. In addition, the method also can be used at various scales for water resources development, regional water resource evaluations, and environmental assessment. Key words: Hydrogeochemical, Groundwater, Salinity, Taounate, Morocco. Cite this Article: Ahmed El Bakouri, Khadija El Kharrim, Mohamed Tayebi and Driss Belghyti, Geochemistry, Quality Appraisal of Groundwater and Hydrogeochemical Process in Middle Ouerrha, Taounate, Rif – Morocco.. International Journal of Civil Engineering and Technology, 10(04), 2019, pp. 15381547 http://www.iaeme.com/IJCIET/issues.asp?JType=IJCIET&VType=10&IType=04 1. INTRODUCTION Groundwater is the major source of fresh water for drinking, irrigation, and other economic sectors [1, 2]. Day by day groundwater reserves are being depleted due to numerous natural and anthropogenic cause. The physicochemical properties of water are influenced by the various natural factors. They are climatic factors [3, 4], hydrological characteristics [5, 6], topography and lithological factors [7]. The decline and degradation of its quality are not easily perceived. Generally they come in addition to easily accessible surface waters. In addition, drought is one of the most important phenomena resulting from climate variability and change. Faced with this situation, it is therefore necessary to launch hydrogeochemical and hydrogeological studies at the regional scale, integrating both the northern and southern part of the Taouante area. 2. STUDY AREA 2.1. Geology The study area with semi-arid climate is located in the Middle Ouerrha basin, in rifaine chain, northernmost part of Morocco, belongs to the alpine building, betico-rifo-tellian from the western Mediterranean. It is separated from the Cordilleras by the strait of Gibraltar. In the Taounate area, Figure 1, the geological formations are complex; we could distinguish several geological systems: Triassic: formed essentially by salt red marls and gypsum. It could be qualified the Allochthonous Triassic. It has been the subject of various tectonic and palaeogeographic interpretations, around the western Mediterranean, especially in the Betic Cordillera in Andalusia [8], as polygenic gypsum matrix breccia of sedimentary origin. Jurassic: the formations are largely developed under two main facies, dolomitic limestones of the Liassic that form large massifs, and a schisto-sandstone flysch of Callovo-Oxfordian. Cretaceous: Characterized by marls and marl-limestone, at the Aptian-Albian the detrital terrigenous character of the sedimentation is accentuated and corresponds to the flysch of Albian-Aptian. http://www.iaeme.com/IJCIET/index.asp 1539 editor@iaeme.com Geochemistry, Quality Appraisal of Groundwater and Hydrogeochemical Process in Middle Ouerrha, Taounate, Rif – Morocco Eocene: The lower and middle Eocene are presented in the form of white flint marls, these outcrops are rare and discontinuous, since in the area of Taounate - Ain Mediouna. Miocene: qualified as ante-nappe in Lower Miocene by a detrital marl-sandstone series, whose outcrops are also widely dispersed. Their sedimentation continues until the end of the Middle Miocene [9]. Quaternary: Quaternary evolution is reflected in the course of the great wadis. 2.2. Stratigraphy In the studied region, the upper Miocene is qualified post-nappe, it normally overcomes the lower Miocene, or rests directly in unconformity on any subrifaine ante-Miocene series. The Upper Miocene formations constitute thick transgressive series on the secondary lands, and fill all the collapsed basins of the Middle Ouerrha. The detailed study of these formations at the level of the Taounate basin makes it possible to distinguish three stratigraphic levels: A basic level, conglomeratic, with rounded elements (pebbles) of varied nature, some of which belong to the underlying Upper Cretaceous, this is a conglomerate that sometimes has a certain bedding marked by the orientation of the small flattened pebbles, Figure 2. The cement of the elements of the conglomerate is of sandstone-sand nature. This basic level consists of three conglomeratic and detrital sandstone bars interspersed with marly levels, Figure 3. A medium level, consisting of a thick series of blue marls with shark teeth. Finally, at the upper level reappear sandy or sandstone detritic formations sometimes conglomerates with however small palettes less bulky than in the basic level. This last level appears slightly discordant could represent the second higher Miocene. Figure 1. Geological map of the study area, Taounate – Morocco http://www.iaeme.com/IJCIET/index.asp 1540 editor@iaeme.com Ahmed El Bakouri, Khadija El Kharrim, Mohamed Tayebi and Driss Belghyti Figure 2. Cross-section in the upper Miocene Formation of Taounate Basin Figure 3. Stratigraphic Log of the Upper Miocene Formation of the Taounate Basin 3. METHODS Groundwater samples were collected from a natural source Hammam and two wells, Kara and Twansa, of different locations in the study area during the period May, August, November 2016 and February 2017. http://www.iaeme.com/IJCIET/index.asp 1541 editor@iaeme.com Geochemistry, Quality Appraisal of Groundwater and Hydrogeochemical Process in Middle Ouerrha, Taounate, Rif – Morocco The analysis of the physicochemical parameters was carried out with the use of some chemicals, materials and some apparatus as: The temperature was measured in situ using an alcohol thermometer. The pH by a pH meter Brand ADWA, model AD1030 with combined electrode. Conductivity (EC) and salinity were determined by an conductivity-meter brand OHAUS, model STARTER ST3100C-F. Ca, Mg, Cl and HCO3 were determined by volumetry. SO4 and NO3 by UV spectrometer Brand SECOMAM, model UVILINE 9400. K and Na were measured by ICP. 4. RESULTS AND DISCUSSION 4.1. Physicochemical characterisation of groundwater The different physicochemical parameters of groundwater are shown in table 1: 4.1.1. Temperature (T) Important factor in all chemical reactions, temperature is an essential element to control all the physicochemical parameters of a given system. It controls the solubility, density and viscosity of water, as well as the speed of chemical reactions. It has a direct effect on the conductivity and pH determination of the water. In the study area, the temperature of the water reaches its maximum value (23 °C) at the Hammam source during the low-water season (August 2016). The minimum value is recorded in the Twansa well of 18.5 °C (May 2016). The temperature difference of 0.5 °C between the Hammam source and the Kara well can be due to the geological formations, since in the Hammam source there is dominance of the limestone rock formations, whereas in the well Kara there are the formations hard schists at the bottom, which appear along the Oued Ouerrha. The difference of 2.5 °C between the Hammam source and the Twansa well is due to the southern exposure of the source and soft marly formations in the Twansa area. 4.1.2. pH The physicochemical equilibrium of a source or a well is essentially determined by the pH. The latter is very sensitive to environmental and geological factors such as, temperature, salinity, lithological nature of the lands crossed, etc. Acidic pH can influence dissolution of salts from the aquifer rocks and increase the metal and TDS load in the groundwater [10]. The spatial and temporal variation in pH shows small fluctuations with average values close to neutrality (7.63), they vary between 7.26 and 7.77 in the Hammam source, between 7.26 and 8.5 in the Kara well and between 7.25 and 7.61 in the Twansa well. This neutral to slightly basic character could be attributed to the sedimentary nature of the mainly carbonate secondary lands formed by limestone, dolomite and marl, hence the buffer effect of the formations, through all the reactions of the potential aquifer system of hydrogen (water/insoluble carbonates/CO2 soluble bicarbonates). This variation in pH is due to the alluvial clay and sand cover that isolates the water table, thus the amount of dissolved salt in the Hammam source and the Kara well, which regulate the acid-base balance of the water. http://www.iaeme.com/IJCIET/index.asp 1542 editor@iaeme.com Ahmed El Bakouri, Khadija El Kharrim, Mohamed Tayebi and Driss Belghyti 4.1.3. Electrical conductivity The measurement of the conductivity is a good appreciation of the degree of mineralization of a water. It is proportional to the quantity of dissolved mineralizable salts. High conductivity in most cases reflects high salinity, which can be of natural origin [11]. The spatial and temporal evolution of the conductivity shows an increasing enrichment in the Hammam source especially during the low-water period which varies between 22700 and 26900 μs/cm, whereas in the Kara and Twansa well it varies between 1510 and 1638 μs/cm and between 3280 and 3700 μs/cm respectively. This high conductivity can be due to a natural origin by leaching of carbonate lithological formations (Gypsum, red salt marl, dolomite, limestone, etc.), hence the release of Ca, Mg, HCO3 etc., especially for the Hammam source. 4.1.4. Salinity Salinity is the mass of salts or ionic compounds dissolved in a liter of water; it is expressed in g/L of water. An ionic compound or crystalline ionic solid consists of positively charged cations and negatively charged anions regularly arranged in space. An ionic crystal is electrically neutral. The salts can be of geogenic origin from rock weathering or anthropogenic origin like urban runoff, sewage, industrial discharge and type of material used in piping for water supply [12]. The salinity of the water varies from one zone to another, it is between 13.68 and 16.51 g/L in the Hammam source, 0.73 and 0.88 g/L in the Kara well and 1.46 and 1.93 g/L in the Twansa well. The high salinity is mainly due to leaching and/or water-rock contact of the saline marl formations of the Tortonian by aquifer waters, Figure 4, while the low mineralization is due to dilution by aquifer waters or the absence of gypsum levels. 4.1.5. Calcium Water is composed of many mineral and organic elements. Its richness in minerals varies according to the composition of the soils it crosses. The calcareous grounds will give a water rich in calcium. Calcium is one of the parameters that contributes to the mineralization of water. It appears that the groundwater of Taounate region, have quite remarkable levels of calcium. They range between 677.4 and 941.2 mg/L in the Hammam source, between 76.9 and 112.2 mg/L in the Kara well and between 108.4 and 176.3 mg/L in the Twansa well. This would be due to the dissolution of the carbonate formations of Mio-Pliocene and alluvial gypsum formations of the Quaternary. 4.1.6. Magnesium Rainwater is very poor in magnesium; the latter comes mainly from the dissolution of carbonate formations with high levels of magnesium (magnesite and dolomite). The kinetics of the dissolution of these rocks is not fast. Since the dissolution time is greater than for calcite, the high levels of magnesium generally indicate slow transit waters. The highest values are observed in the Hammam source during the 2016 summer campaign (383.2 mg/L). 4.1.7. Sodium Sodium can be generated from aquifer water interaction by cation exchange processes or from anthropogenic sources like pollution from wastewater and septic tanks [13]. They results from rapid dissolution and in large amounts of NaCl. Their presence is often very low, it comes from the precipitations which constitute the principal leaching contribution of atmospheric impurities of oceanic origin. The highest values, in the order of 5600 mg/L, are recorded in the http://www.iaeme.com/IJCIET/index.asp 1543 editor@iaeme.com Geochemistry, Quality Appraisal of Groundwater and Hydrogeochemical Process in Middle Ouerrha, Taounate, Rif – Morocco Hammam source. These concentrations are influenced by the contributions due to the presence of triassic formations (salt red marls) at the border of the source, silicate minerals, such as clays or by evaporation, which is active in soils close to the surface which favors the reconcentration of Na+. At the Kara and Twansa wells these concentrations are low compared to the source. They range between 155 and 210.9 mg/L and between 440 and 670 mg/L respectively. 4.1.8. Potassium Potassium concentrations range from 14.6 to 25 mg/L in the Hammam source, 5.2 to 6 mg/L in the Kara well and 1.7 to 2.1 mg/L in the Twansa well. The presence of potassium in water is linked to the alteration of potassium clays, the rapid and high dissolution of KCl. Potassium is not very mobile in the surface environment and most anthropogenic inputs will be consumed by biomass or through reactions involving clay minerals. It is an element that may have a significant anthropogenic signal from agrochemicals or organic fertilisers [14]. 4.1.9. Bicarbonates Bicarbonate alkalinity seems to be the major source of alkalinity of groundwater, due to the dissolution of CO2 and carbonates, oxidation of organic matter [15] and reaction of silicates with carbonic acid [16]. The concentration of bicarbonates in water is a function of the temperature of the water, the tension of dissolved CO2, the concentration of water in salts and the lithological nature of the lands crossed. Significant concentrations occur in the Twansa zone with contents ranging from 411.8 to 549 mg/L. In Hammam the concentrations are relatively low because the chloride facies is the most dominant. 4.1.10. Sulphate Sulphate concentration in groundwater usually remains low due to reducing conditions in the aquifers, which inhibits sulphide oxidation [17]. The variability of sulphate levels observed in groundwater is of great hydrogeological interest. Their origin is related to the precipitation, which can contain significant quantities of SO4, or to the leaching of the evaporitic rocks (gypsum, anhydrite, etc.). The highest value is recorded in the Hammam source of 1710 mg/L. The lowest is 137 mg/L in the Kara well. According to WHO the limit value is 250 mg/L, which makes the Hammam source undrinkable. 4.1.11. Chloride Chloride concentrations are high and reach very high values, especially at the Hammam source. They range between 8260.5 and 9005 mg/L, especially during the low-water period, whereas in the Kara and Twansa wells these concentrations vary between 215.2 and 244.6 mg/L and 804.8 and 885.6 mg/L respectively, which is the acceptable limit for chloride is 250 mg/L (WHO). These high values are due to the leaching of dolomitic marls and limestones on the one hand and the leaching of Quarternary sediments covering the sector on the other hand. The presence of alluvium and evaporitic sediments on the soil surface facilitates leaching. During periods of low water, intense evaporation influences the levels, especially when the piezometric level is close to the ground surface. 4.1.12. Nitrates In natural conditions, the nitrate concentration does not exceed 10 mg/l in the water [18] so nitrates concentration, beyond the 10 mg/L, is an indicator of anthropogenic pollution. They represent the most oxygenated form of nitrogen and are highly soluble. The maximum level is http://www.iaeme.com/IJCIET/index.asp 1544 editor@iaeme.com Ahmed El Bakouri, Khadija El Kharrim, Mohamed Tayebi and Driss Belghyti observed during the August 2016 outbreaks (19 mg/L in the Kara well and 25.7 mg/L in the Twansa well). These high levels are due to the agricultural activities that control the migration of nitrates from the soil surface to the roof of the aquifer through the unsaturated zone and its subsequent movement in the aquifer. a) Hammam b) Twansa Figure 4. The leached salts in the study area, Taounate – Morocco Table 1. Results of water sample analysis of study area in May, August, November 2016 and February 2017; T as °C, EC as µs/cm, Salinity as g/L, and other ions as mg/L (HS: Hammam source, KH: Kara wells, TW: Twansa Wells) ID T pH EC Salinity Ca2+ HS 21 7.77 22700 13.68 KW 20.5 7.89 1510 0.73 TW 18.5 7.58 3280 1.65 677.4 76.9 160.6 HS 23 7.26 26900 16.51 KW 22.5 7.26 1631 0.88 TW 20 7.25 3510 1.83 696.8 85.3 176.3 HS 21.5 7.54 25800 15.79 KW 21 7.77 1638 0.88 TW 19 7.47 3430 1.46 941.2 102.2 108.4 HS 21 7.67 23300 13.94 KW 20.5 8.5 1598 0.78 TW 19 7.61 3700 1.93 701.4 112.2 168.3 Cations Na+ May 2016 331.3 5600 41.9 160 44.2 670 August 2016 383.2 4900 50.9 170 38.3 440 November 2016 111.2 3950 41.7 210.9 63.6 530.9 February 2017 159.3 3760 37.5 155 61.3 610 Mg2+ + K HCO3 Anions SO42− Cl− 24 5.2 1.7 284.5 365.4 443 1396 8260.5 24.4 185.9 226.9 17.3 253.3 840.2 25.3 25 6 1.8 250.1 1047.1 9005 1.9 347.7 249.8 215.2 19 411.8 285.8 804.8 25.7 15.6 5.9 1.7 14.6 5.6 2.1 − 329 402 549 NO3− 1710 8979.7 1.9 137 218 4.87 155.5 885.6 5.76 335.5 1425 344.65 216.5 437.37 314 8296 0.85 244.6 9.48 872.1 9.88 4.2. Correlation For the correlation analysis ± 0.9 ≤ r2 ≤ 1 was considered as strong, 0.9 ≤ r2 ≥ 0.5 as moderate and r2 ≤ ± 0.5 as poor [19]. Salinity is strongly correlated with Cl−, Na+ and SO42−, Figure 5. However, Cl− and SO42− show stronger correlation signifying these is the most significant parameter for salinity, regulated by hydrogeological and climatic factors as well as anthropogenic factors in unconfined groundwater. In particular, evaporation (a climatic factor) is very intense in the area. In addition, hydrogeological (weathering and water-rock http://www.iaeme.com/IJCIET/index.asp 1545 editor@iaeme.com Geochemistry, Quality Appraisal of Groundwater and Hydrogeochemical Process in Middle Ouerrha, Taounate, Rif – Morocco interactions) and anthropogenic factors (agricultural activities) contributed to increasing major anion concentrations [20]. For K+, Ca2+ and Mg2+ showed moderate correlation with salinity, which in this system originated mainly from the dissolution of mineral such as carbonates and gypsum [21]. HCO3− and NO3− showed poor correlation with salinity. This signifies that prevalence of Na-rich bicarbonates sources and less chance of halite sources [22]. Finally, it is evident that dissolution of minerals due to aquifer water interaction plays a major role in groundwater quality in the Taounate area. Figure 5. Correlation 5. CONCLUSION From the analysis and discussion of the results, it is concluded that the main reason for the deterioration of the water quality of Taounate area, is the high salinity. In the aquifer, groundwater may be ascribed to evaporation and soil salts dissolution, whereas high salinity in confined groundwater is caused by water-rock interactions, controlling the groundwater chemistry of the area by the precipitation of calcite and dolomite, dissolution of silicate minerals, salt red marl and gypsum, and cation exchange, which increased SO4 concentrations locally. Most of the maximum concentrations are recorded at the Hammam source, of SO4·Cl– Na type, with cations ordered as Na+ > Ca2+ > Mg2+ > K+ and anions ordered as Cl− > SO42− > HCO3− > CO32−. It is suggested that an appropriate mechanism be established for continuous monitoring of the water resources for its hydrochemistry and hydrology so that a strategy and action plan is developed for the conservation and restoration of this important resource. 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