A Preliminary Assessment of Hydrogeochemical Quality of Groundwater around Rural Communities of Abandoned Nkalagu Limestone Quarry. SE Nigeria

The study was conducted with the aim of assessing factors that influence groundwater geochemistry within the study area. Twenty-seven (27) groundwater samples were collected for major cations and anions were analysis. From the results obtained, it was observed that pH value fell within the slightly acidic to basic, values obtained from total dissolved solid showed that twenty six (26) groundwater samples fell within fresh water category, while one (1) groundwater sample fell within brackish water category, electrical conductivity ranges from 16.21 to 1136 µ S/cm. The study revealed that ion exchange and rock weathering are the major geochemical processes that influence groundwater chemistry within the study area. Parson plot revealed that groundwater samples are of different water type; Na-SO 4 , Na-Cl, Ca-Mg-SO 4 and Ca-Mg-Cl water type. Relationship between Na + /Cl¯ versus Ca 2+ / (HCO 3 ¯ + SO 42 ¯ ) showed that groundwater was classified under natural state. TDS versus TH plots revealed that groundwater within study area falls within soft-fresh water category, except sample NA-18. Finally, deduction from Soltan classification revealed that sample locations; NA-01, 02, 03, 04, 06, 07, 08, 10, 11, 12, 13, 15, 16, 17, 19, 21, 22, 23, 24 and 27 were classified under deep meteoric water type, while NA-05, 09, 14, 18, 20, 25 and 26 were classified shallow meteoric water type.


The Study Area
Location, climate, geology and hydrogeology  [10].

Sampling Points
The study area is located in the Sub urban area of Abakaliki, Ebonyi state, southeastern Nigeria. It lies between latitudes 6°15′ and 6°35′N and longitudes 7°39′ and 8°00′E. The area is quite accessible through a network of major roads and footpaths as shown in Figure 1.

Vegetation and climate
The study area belongs to the rainforest region of Nigeria as described by Igbozuruike [13]. The vegetation is characterized by orchard bush of short trees with varying densities of dominant elephant grasses. Two major seasons are experienced in the areathe wet and dry season. The wet season starts from March and ends in October, while the dry season begins in November and ends in February. These two seasons are dependent on the two prevailing winds blowing across the country at different times of the year-the dry harmattan Wind, the North East Trade Wind from the Sahara Desert that prevails in the dry season and the marine wind, the SW Trade Wind, from the Atlantic Ocean which introduces the rainy season. Temperature in the dry season and rainy season ranges from 20 to 38 °C and 16 to 28 °C, respectively. The average monthly rainfall ranges from 3.1mm in January and 270mm in July. The average annual rainfall varies from 1750 to 2250mm. The climate of the area, no doubt, favors the dispersion of the resultant pollutants from the mining activities. Eyankware et al. [10] stated that high amount of rainfall results in surface run-of that moves the pollutants and also assists percolation. The drainage pattern of the area is dendritic.

Geology and hydrogeology of the study area
The Benue Trough is a linear NE-SW trending trough that is divided into three parts, namely the Upper, Middle and Lower parts [14,15]. Sedimentation in the Abakaliki Basin of the Lower Benue Trough started with deposition from the Asu River Group of Upper Albian age which overlies the Precambrian Basement Complex rocks dis-conformably as shown in Table 1. The Asu river group consists of Abakaliki Shale with volcano clastics, sandstone and sandy limestone lenses [16]. The Asu River Group is overlain by the Eze-Aku Formation of Turonian age. This formation consists of flaggy, grey or black shales with sandstones and subordinate limestone [17]. An alternating sequence of thick limestone or sandstone units occurs with calcareous shales in places where the Eze-Aku Formation is found [18]. The hydrogeology of the study area is typified by poor aquifer conditions. This is a result of the dominant shale units (Aquiclude) which are neither porous nor permeable and do not transmit water to wells found in the area. Eyankware et al. [10] further pointed out that groundwater on a regional scale is impossible to find. However, conditions for the presence of groundwater may occur at weathered/fractured zones or at points of sandstone intercalations. The structure and hydrogeology of the fractured aquifer in the study area are typical of a multilayer complex system. The water bearing formation within the study area exists in fractured shale and limestone [19]. The major sources of water are stream, hand-dug well, manual borehole and motorized borehole ( Figure 2). pH The pH of water is an important parameter which shows the level of acidity or alkalinity of the water body. In other words, it furnishes information on the hydrogen ion concentration of natural water. From the Table 1, the measured pH is found to be slightly acidic to basic and ranges from 6.3 to 7.9 with mean value of 7.15 with an average value of 6.89 as shown in Table 1.

Soltan classification
The sources of groundwater have been classified into two types by Soltan [23]. The classifications are based on base-exchange indices (r1) and meteoric genesis indices (r2) as presented in equations 1a and 1b.

Results and Discussion
Total dissolved solid (TDS)  The results of geochemical analysis indicated that TDS ranges from 21.09 to 1093mg/L with mean value as 498.93mg/L ( Table  1). Table 2 shows that groundwater samples within the study area fell within freshwater category except NA-18 that fall within brackish water type which could be considered to be more salty when compared to fresh water type (Figure 3). Various factors are responsible for diverse value of TDS, these include geological, climatic and human factors [12,[23][24][25][26].

Electrical conductivity (EC)
The value of EC ranges from 16.21 to 1136µS/cm with average value of 626.9µS/cm ( Table 1). The area of high concentration of EC (NA-06, 07, 15, 16 and 19) shows that groundwater is in contact with more dissolved inorganic constituents.

Ion exchange
Factor controlling groundwater chemistry was also evaluated using bivariate diagrams such as Mg against Ca +Mg, Ca + Mg versus HCO 3 +SO 4 , Na versus Ca, Cl versus Na, SO 4 versus Ca, Mg versus Ca, Na/Cl versus EC as widely used (Figure 4-10) respectively. Jong et al. [27] stated that during the rock weathering the composition of various cation and anion might be changed, and the number of cations is dependent on the rock mineralogy. In most cases, the source rock minerals may be deduced from the groundwater composition. The Mg 2+ to Ca 2+ ratio approaches one, it is very likely that Ca 2+ has been removed from the solution and this process is commonly called dedolomitization. Hounslaw [28] suggest that when Mg 2+ is greater than (equal or less than) Ca 2+ , there

ACSR.000522. 1(5).2019
are four possibilities such as: 1) Gypsum dissolution (=0.5); 2) Limestone-dolomite weathering (<0.5); 3) Dolomite dissolution, calcite precipitation. In Figure 4, we can understand that there are all possibilities as mentioned above during the weathering and dissolution processes. The scatter diagram of Ca+Mg vs HCO 3 +SO 4 ( Figure 5) shows that samples are equiline 1:1, indicating that silicate and carbonate weathering are the primary process involved in the evolution of groundwater [29]. The Na vs Ca plot indicates that most of the samples lie slightly below the equiline ( Figure 6). The excess of Na is attributed to carbonate weathering. Na versus Cl can be used to identify the evaporation process in groundwater [29]. Evaporation will increase the concentration of TDS in groundwater, and Na/Cl ratio remains same, and it is one of the major indicators of evaporation. Chebbah [30] further stated that if evaporation is the dominant process Na versus Cl against EC would give a horizontal line, this could be attributed to the fact that evaporation and evapotranspiration is an effective indicator (Figure 7). In the plot for Na/Cl vs. EC Figure 8 the Na/Cl shows a decreasing trend with increasing EC along with higher Na/Cl ratio, it reveals that Na released from silicate weathering process. Morever, in SO 4 versus Ca it was observed that distrubution of the samplesare in equiline 1:1. This shows that carbonate and silicateweathering are the major process that influences geochemical constiutent of groundwater within the study area (Figure 9). This is inline with Eyankware et al. [4] which stated that weathering has major influence on geochemistry of groundwater within the asu river group of lower benue trough nigeria.

Hydrogeochemical classification
From Figure 10 it was observed that groundwater sampling points were categorized into four water type: Na-SO 4 , Na-Cl, Ca-Mg-SO 4 and Ca-Mg-Cl water type. Sample locations NA-11, 15, 20 and 23 are classified as Na-SO 4 water type, NA-10, 13, 14 and 22 were classified as Na-Cl water type, NA-01, 02, 03, 04, 07, 09, 18 and 26 were classified as Ca-Mg-SO 4 lastly NA-05, 06, 08, 12, 16, 17, 19, 21, 24 and 27are classified as Ca-Mg-Cl water type. This infers that groundwater is of different origin. Figure 11 shows the relationship between Ca 2+ / (HCO 3¯ + SO 4 2¯) versus Na + /Cl¯. The distribution of samples indicates sampling points were categorize under natural state, that implies that natural salt dissolution such as carbonates and silicate weathering is the main processes controlling groundwater composition in the study area. The plot of TDS versus TH revealed that groundwater sample points within the study area fell within soft-fresh water category, except sample NA-18 that fell within soft-brackish water. Reasons for soft-fresh water could be attributed to low concentrations of Ca 2+ and Mg 2+ (Figure 12). Sample NA-18 is believed to be saltier compared other sampling points.

Conclusion
This study incorporates the governing processes that influence groundwater chemistry. Results revealed that pH fell within slightly acidic to basic, TDS values showed sampled points were classified under fresh water except for NA-18 that falls within brackish water. Ion exchange deductions revealed that dissolution, rock weathering, ion exchange were the major factors that influences hydrogeochemical process of groundwater within the study area. The mechanism of these actions and diverse mineralization processes as well as their combination had given rise to the salinity of groundwater within the area of study. Parson Plot further revealed that groundwater is of different origin. Relationship between Na + /Cl¯ versus Ca 2+ / (HCO 3¯+ SO 4 2¯) showed that groundwater within natural state. Plot of TDS against TH revealed that 99.9% groundwater within the study area fell with soft-fresh water category. Soltan classification showed that larger percentage of groundwater within the study area were classified within deep meteoric water type.