ARID ZONE JOURNAL OF ENGINEERING, TECHNOLOGY & ENVIRONMENT AZOJETE December 2023. Vol. 19(4):793-806 Published by the Faculty of Engineering, University of Maiduguri, Maiduguri, Nigeria. Print ISSN: 1596-2490, Electronic ISSN: 2545-5818 www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 793 HYDROCHEMISTRY OF SURFACE AND GROUNDWATER IN PARTS OF BIRNIN KEBBI NORTHWESTERN NIGERIA Y. Abdulganiyu1*, B. S. Oresajo1, M. AbdulKarim1, O. A. Phillips1, H. Ibrahim1, T. A. Abdulfatah1, H. Yakubu1, H. Zainab1, M. Sadiya1, A. Nasiru1 and I. Mahmud2 1Department of Geology, Federal University Birnin Kebbi, Kebbi State, Nigeria 2Department of Geology, Federal University Dutsinma, Katsina State, Nigeria *Corresponding author's email address: charger.ca34@gmail.com ARTICLE INFORMATION Submitted 30 March, 2023 Revised 3 Sept, 2023 Accepted 9 Sept, 2023 Keywords: Water type Physico-chemical heavy metal Nemerow’s pollution index contamination ABSTRACT A hydro-chemical investigation of drinking water sources in Birnin Kebbi Old Town and its environs, in northwestern Nigeria, was carried out to determine the potability and suitability of the groundwater for domestic and agricultural uses. Twenty-three water samples were collected from these communities, and their physical and chemical parameters, such as electrical conductivity, total dissolved solids, pH, and temperature, were evaluated. Both the chemical and heavy metal analyses were conducted at the Multi-User Laboratory, Usmanu Danfodiyo University, Sokoto. The results obtained indicated that physical parameters like TDS and EC and chemical parameters like Mg2+, Ca2+ and HCO3 2- are high, while Cr2+, Fe2+, Ni, and Pb2+ have values that are below the NSDWQ recommended limits. While Na2+, Cu2+, Cl-, and NO3 - have values far below the NSDWQ set limit, The Schoeller and Piper diagrams show the dominant water type in the study area to be Ca-Mg-HCO3. However, the Gibbs plot shows the dominant source of the water to be the precipitation domain due to the dissolution of carbonate rocks, while the Wilcox diagram shows that all the water samples in the study area have low salinity. Application of Nemerow’s pollution index method shows that the majority of the sampling locations displayed high NPI values, especially for Ni2+ and Pb2+. The NPI Ni2+ values for eleven (11) out of twenty-three samples, making up 47.83%, have NPI values that range from 7.53 to 90.01, making them unsuitable for drinking purposes. The NPI values for Pb2+ for six (6) samples, making up about 26.09%, have high NPI values that range from 36.37 to 172.56, depicting a high level of pollution 1.0 Introduction Groundwater is a valuable resource in the vast, thickly populated, semi-arid and arid areas of Kebbi State, northwestern Nigeria, and where it is available, it is unreliable. Because improved water supply is one of the essentials for a healthy lifestyle, it is constrained by uncontrolled anthropogenic activities (Chen, et al. 2016; Chitsazan et al., 2019), flow of pollution from upland to lowland, too much use of fertilizers, pesticides in agriculture (Joarder et al., 2008) and to some extent by natural conditions (Zadawa and Omran, 2018). Since surface and groundwater quality has become an important water resources issue due to rapid population increase and unplanned urbanization. Pollution Index become a powerful tool for processing, analyzing, and conveying raw environmental information to decision makers, and the public (Caeiro et al., 2005). Highly toxic elements, including mercury, lead, arsenic, cadmium and nickel have been established as dangerous surface and groundwater pollutants which pose great health risks, especially in rural communities that directly utilize these resources (Burke, 2016). Boreholes and dug wells are used to abstract groundwater in addition to water from the River Dukkul, which passes through most of the study area (Figure 1). Notable earlier workers on the hydrogeology of the study area include Raeburn and Tattam (1930), Du Preez and Barber (1965), Anderson and Ogilbee (1973), Adelana et al. (2003), Alagbe (2006), and Kwaya et al. (2020) and Oteze (1976, 1991). Oteze (1976) indicated that the Kalambaina aquifer, which is http://www.azojete.com.ng/ mailto:%20odumaoke@gmail.com mailto:%20charger.ca34@gmail.com mailto:%20charger.ca34@gmail.com Arid Zone Journal of Engineering, Technology and Environment, Dec, 2023; Vol. 19(4):793-806. ISSN 1596-2490; e-ISSN 2545-5818; www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 794 shallow and cavernous, is readily subjected to pollution from human and animal wastes. But Wali et al. (2020) concluded that both Illo and Gwandu formations display significant differences in their physicochemical parameters of water quality and mineral facies of rock weathering This work is to employ hydrochemistry and Nemerow pollution index (NPI) to determine the suitability of the surface and groundwater in the study area for domestic and agricultural uses. This study employed hydrochemistry to determine the suitability of surface and groundwater in the study area, while the Nemerow pollution index (NPI) is to determine the heavy metal pollution status of the surface and groundwater in the study area. 2. Materials and Methods 2.1 Study Area The research was carried out within Birnin Kebbi old town and several other villages, which form part of the Birnin Kebbi Sheet 49, northwestern Nigeria. The study area is part of Gwandu Formation and is accessible through Birnin Kebbi - Dukkul road, Birnin Kebbi -Zauro, Badariya - Kola road with several foot paths and untared roads. The relief of the study area consists of flat-topped hills with ironstone capping which is dominated by gullies which serves as drainage to some of the surrounding villages. Generally, the hills are less than 150 feet high, but the relief between the stream valley floor (Fadama) and the hill tops reaches 300 feet. South and east of the Sokoto Basin, crystalline rocks form a dissected upland surrounded by isolated steep sided hills (Anderson and Ogilbee, 1973). The study area is drained by River Dukku and its tributaries which provide extensive floodplains for farming activities as shown in (Fig 1) flowing northwest direction. The study area is located within the semi-arid zone of northwestern Nigeria, with two distinct seasons characterized with rainy and dry conditions. These are characterized by a short period of rainfall that really exceeds 5 months with a yearly average precipitation of about 600 mm. The rainfall is erratic with longer dry season that lasted from October to April, characterized by high temperature, low humidity with high evapotranspiration which can exceed 2,500 mm/year. Vegetation is the savannah-type and is characterized by sparse shrub and short feathery grasses, which forms a complete ground cover during the wet season only. The study area is part of the Nigerian sector of the Iullemmeden Basin in north-western Nigeria which is underlain by a sequence of semi-consolidated sedimentary rocks ranging in age from Cretaceous to Tertiary and consisting mostly of interbedded sand, clay, and limestone. The stratigraphy of the basin is made up of the Taloka, Dukamaje, Wurno, Dange, Kalambaina, Gamba and Gwandu Formations. The sediments were deposited during four main phases: 1. The Illo and Gundumi Formations are composed of grits and clays, which were deposited unconformably on the Pre-Cambrian Basement. 2. The Maastrichtian Rima Group rests unconformably on the Illo and Gundumi Formations. The group consists of mudstones and friable sandstones (Taloka and Wurno Formations), separated by the fossiliferous Dukamaje Formation. 3. The Paleocene Sokoto Group consists of the Dange and Gamba Formations (mainly shale) and is separated by the calcareous Kalambaina Formation. 4. The Post-Paleocene Continental Terminal, which is the Gwandu Formation, occurs as tabular hills or low hummocks over the dip slope of the Paleocene Formation. The study area is predominantly of the Gwandu Formation. file:///C:/user/Downloads/azojete143/www.azojete.com.ng mailto:%20odumaoke@gmail.com Abdulganiyu et al: Hydrochemistry of Surface and Groundwater in Parts of Birnin Kebbi Northwestern Nigeria. AZOJETE, 19(4):793- 806. ISSN 1596-2490; e-ISSN 2545-5818, www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 795 2.2 Data Collection and Analysis Twenty-three groundwater and surface water samples taken from dug wells, tube wells, rivers, and boreholes were collected from different communities within the study area and subjected to hydrogeochemical analyses to determine the different physicochemical parameters present in the water samples. The APHA (1999) criteria were followed for sampling, handling and analysis. Electrical conductivity (EC), Total dissolved solids (TDS), pH, and temperature were measured in the field using a hand-held portable digital 3-in-1 conductivity metre and a pH metre, respectively. The samples were stored at a very low temperature of < 4oC and transported to the multi-user laboratory of Usmanu Danfodiyo University, Sokoto, where they were processed and analyzed for major and minor cations, anions, and oxides using an atomic absorption spectrometer (AAS). Nemerow Pollution index (NPI) was used to determine the pollution level since ground and surface water quality has become an important water resources issue due to rapid increase of population and unplanned urbanization. Sample points with their respective coordinates are displayed in Table 1. Twenty-three samples were collected in all, with groundwater (14) taken from dug wells, tube wells and boreholes, while nine (9) surface water samples were collected from the River Dukkul in the study area (Figure 1 and Figure 2) in different communities within the study area (Table 1a). The APHA (1999) criteria were followed for sampling, handling and analysis. Prior to the sampling, the containers were rinse with water from which the samples were to be collected; in order to get representative samples, direct from the aquifer. Water was pumped out or bailout using a water drawer from the different groundwater sources for at least 10 – 15 minutes. Two samples were collected from each of the sampling points, in one sample from which the cations were to be analyzed and few drops of 1.1 molar HNO3 was added to reduce the precipitation of some metals by reducing the pH of the water to 2. Physical parameters of electrical conductivity (EC), total dissolved solids (TDS) pH, and temperature were measured in-situ at the sampling points using a handheld 3-in-1 conductivity and pH meters, respectively. Samples were stored at a very low temperature of 4o C. The samples were taken to the multi- user laboratory of Usmanu Danfodiyo University, Sokoto, where they were processed and analyzed for major and minor cations, anions, and oxides using an atomic absorption spectrometer (AAS model AA 6300 SHIMADZU Japan). The Piper and Schoeller plots were employed for the samples to know the water types and the level of contamination and relative concentration of the anions and cations in the study area. While the Wilcox diagram and Gibbs plots were used to know the level of salinity and to define the source of the chemical species in the analyzed water samples in the study area. Statistical analyses were used to evaluate the heavy metals and the physical parameters measured in the study area using IBM SPSS 2.1 model software statistical package. Nemerow Pollution index (NPI) was used to determine the pollution level since ground and surface water quality has become an important water resources issue due to rapid increase of population and unplanned urbanization. http://www.azojete.com.ng/ mailto:%20odumaoke@gmail.com Arid Zone Journal of Engineering, Technology and Environment, Dec, 2023; Vol. 19(4):793-806. ISSN 1596-2490; e-ISSN 2545-5818; www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 796 Figure 1: Drainage map of the study area. TABLE 1: Community drinking water source analyzed samples with coordinates. Sample Number Names of Location with their coordinates Drinking Water Source 1 Takalau N 12° 28' 12'' E 4° 11' 16'' Borehole 2 Takalau N 12° 28' 08'' E 4° 11' 19'' Well 3 Takalau N 12°28' 11'' E 4° 11' 29'' Well Ii 4 Water Works N 12° 28' 53'' E 4° 12' 2'' River Dukul 5 Gamagira N 12° 27' 57'' E 4° 11' 30'' Borehole 6 Malala Quarters N 12° 28' 16.8'' E 4° 11' 13.1'' Borehole 7 Fadama Ii N 12° 28' 46.5'' E 4° 11' 22.7'' River Dukul 8 Fadama Ii N 12° 28' 46.5' E 4° 11' 22.7'' River Dukul 9 Tarasa I N 12° 28' 42'' E 4° 10' 23'' Well 10 Dutsen Idi N 12° 28' 01'' E 4° 11' 24'' Borehole 11 Tungar Buzu N 12° 29' 40'' E 4° 16' 23'' Well 12 Tungar Buzu N 12° 29' 57'' E 4° 16' 15'' River Dukul 13 Tarasa Ii N 12° 28' 33'' E 4° 9' 46'' River Dukul 14 Unguwar Jodu N 12° 26' 7.8'' E 4° 7' 36.3'' Well 15 Tarasa Iii N 12° 28' 36'' E 4° 10' 10.7'' River Dukul 16 Gamagira(Dangaladima) N 12° 28' 11'' E 4° 11' 24'' Borehole 17 Tarasa N 12° 28' 44'' E 4° 9' 34'' Tube Well 18 Gwadangwaji N 12° 28' 31.1'' E 4° 13' 53.7'' Bore Hole 19 Water Works Ii N 12° 28' 53'' E 4° 12' 2'' River Dukul 20 Tarasa Iv N 12° 26' 56'' E 4° 10' 31'' Borehole 21 Takalau N 12° 28' 11'' E 4° 11' 24'' Borehole 22 Tarasa V N 12° 28' 44'' E 4° 9' 41'' River Dukul 23 Tarasa N 12° 28' 44'' E 4° 9' 41'' River Dukul Table 1b: Equation used for pollution indices computation for water samples collected from study area. file:///C:/user/Downloads/azojete143/www.azojete.com.ng mailto:%20odumaoke@gmail.com Abdulganiyu et al: Hydrochemistry of Surface and Groundwater in Parts of Birnin Kebbi Northwestern Nigeria. AZOJETE, 19(4):793- 806. ISSN 1596-2490; e-ISSN 2545-5818, www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 797 3. Results and Discussion The results of the physical parameters measured in the study area are presented in Table 2. For the 23 surface and groundwater samples analyzed, the measured temperature ranged between 33.3 and 34.2oC. pH values ranged between 0.27 (sample L16A from DanGaladima) and 7.32 (sample 4A from the waterworks). The pH of the water in this study indicated weakly acidic to slightly alkaline water because the former samples were from a borehole located 4 m from a pit latrine, while the latter were from near the waterworks, where dry season farming with excessive fertilizers occurs. The EC measured ranges between 70 and 9692, while the TDS fluctuates between 35 and 5501. The variation observed in these physical parameters is due to uncontrolled anthropogenic activities in the study area, mainly agricultural activities and improper waste disposal. However, most of the physical parameters measured values fall within the acceptable limit of WHO (2011), as given in Table 2. The geological map of the study area is displayed in Figure 2. The results of the major elements and oxides measured for the samples Table 3, which was used in plotting the Piper diagram, Schoeller plot, Gibbs diagram, and Wilcox diagrams The Piper diagram was used to classify the hydro-chemical facies of the groundwater according to the dominant ions analyzed in the samples. The dominant water type in the study area is Ca- Mg-HCO3. Figure 4 3, which can be attributed to the presence of Ca2+, Mg2+, and HCO32-, which are dissolved in the water from the breakdown and dissolution of carbonate rock, mainly limestone, which occurs in the area. However, the results of heavy metals measured for samples in the study area are shown in Table 4 and Table 5 display summary of physical parameters and heavy metals measured in the study area. Figure 2: a. Generalized geological map of the Nigerian sector of Iullemmeden Basin (Sokoto Basin) showing the study area (red). b. Geological map of the study area. http://www.azojete.com.ng/ mailto:%20odumaoke@gmail.com Arid Zone Journal of Engineering, Technology and Environment, Dec, 2023; Vol. 19(4):793-806. ISSN 1596-2490; e-ISSN 2545-5818; www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 798 Table 2: Physical parameters for the water samples measured in the field Sample Number Ec Tds Ph Temperature (℃) 1a 936 469 6.34 34.2 2a 590 295 5.46 33.7 3a 1638 819 6.76 34.2 4a 114 57 7.32 33.4 5a 916 458 6.94 33.3 6a 3562 1781 1.63 34.2 7a 112 56 6.09 33.5 8a 114 57 6.59 34.2 9a 114 57 7.01 33.8 10a 1244 622.4 0.59 34.2 11b 90 45 4.14 33.8 12b 112 56 6.2 33.7 13a 114 57 6.55 33.8 14a 92 46 6.36 34 15a 114 57 6.81 34.2 16a 1506 5501 0.27 33.8 17a 416 217 5.46 33.8 18a 192 96 5.19 33.8 19a 9692 4846 0.85 33.9 20b 070 035 3.52 34 21a 312 156 5.47 33.7 22a 134 67 5.51 33.7 L 23 90 45 6.08 33.8 Average 968.4348 691.1043 5.093043 33.85652 Maximum 9692 5501 7.32 34.2 Minimum 70 35 0.27 33.3 Table 3: Major elements and oxides measured in the laboratory. Sample Number Mg/L Ca Mg/L Mg Mg/L K Mg/L Na Mg/L P Mg/L Co3 Mg/L Hco3 Mg/L Cl Mg/L Nh4 Mg/L No3 1a 166 194.4** 20** 6.7 0.19 Nil 72 0.6 0.4 2.0 2a 102 87.6 5.2 3.8 0.19 Nil 60 1.1 0.4 1.2 3a 268** 67.2 26 20 0.20 Nil 92 0.7 0.8 2.4 4a 84 74.4 0.7 0.8 0.22 Nil 52 1.6 0.4 1.4 5b 64 79.2 7.4 8.3 0.21 0.2 124** 1.9 0.6 1.8 6a 112 100.8 2.4 3.3 0.20 Nil 64 0.7 0.4 1.0 7b 46 76.8 0.8 0.9 0.22 Nil 64 2.6 0.6 1.4 8b 72 54.0 0.7 0.9 0.22 Nil 80 2.1 0.4 1.2 9a 108 51.6 0.7 0.9 0.23 Nil 96 1.2 0.8 1.6 10a 68 109.2 2.2 2.5 0.19 0.2 76 0.6 0.4 1.0 11b 74 73.2 0.6 0.6 0.19 Nil 84 0.6 0.4 1.0 12b 286** 5.04 0.6 0.8 0.21 Nil 104** 1.7 0.4 1.4 13a 56 56.4 0.7 1.0 0.22 Nil 112 1.4 0.4 1.4 14a 90 51.6 1.9 0.9 0.19 Nil 68 0.5 0.4 1.0 15a 68 78.0 0.7 1.0 0.21 Nil 52 1.9 0.8 1.8 16a 286** 135.6 5.8 8.3 0.19 Nil 136** 0.5 0.4 1.0 17a 134 126.0 2.6 3.9 0.19 Nil 92 0.7 0.6 1.4 18a 72 78.0 0.8 1.7 0.19 Nil 108 0.7 0.4 1.4 19a 114 100.8 0.7 1.5 0.20 0.2 148** 3.2 0.4 2.2 20b 96 62.4 0.6 0.8 0.19 Nil 76 0.6 0.8 1.4 21a 84 73.2 7.0 1.3 0.19 Nil 96 1.0 0.4 1.2 22a 66 62.4 0.7 1.1 0.21 0.2 64 2.2 1.0 3.4 23 52 78.0 1.7 0.9 0.19 0.2 108** 0.8 0.6 3.0 Maximum 286 194.4 26 20 0.23 0.2 148 3.2 1.0 3.4 Minimum 46 5.04 0.6 0.6 0.19 0.2 52 0.5 0.4 1.0 Average 111.652 81.558 3.935 3.126 0.2017 0.2 88.174 1.257 0.5304 1.5913 Who 2011 200 150 12 50 120 100 250 50 Nswqs 2007 - - - 200 - - 250 50 file:///C:/user/Downloads/azojete143/www.azojete.com.ng mailto:%20odumaoke@gmail.com Abdulganiyu et al: Hydrochemistry of Surface and Groundwater in Parts of Birnin Kebbi Northwestern Nigeria. AZOJETE, 19(4):793- 806. ISSN 1596-2490; e-ISSN 2545-5818, www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 799 Figure 3: Type classification for water samples from the study area using the Piper trilinear diagram (Back and Hanshaw 1965). A = Calcium type, B = sodium or potassium type, C = magnesium type, D = no dominant type, E = bicarbonate type, F = chloride type, G = sulphate type, H = no dominant type I = Ca+Mg type, J = HCO3 +CO3 type, K= Na+K type, L = Cl+SO4 type M = Ca(Mg) HCO3 type, N = Ca(Mg) Cl SO4 type, O = Na(K) HCO3 type, P = Na(K) Cl(SO4) type. The Piper and Schoeller plots for the samples indicate the dominance of Ca+Mg-HCO3 water in the study area. The level of contamination and relative concentration of the anions and cations in the study area indicate shallow fresh groundwater that is slightly hard. The water is associated with limestone underlining the area and carbonate hardness from recent precipitation occurring at shallow depths below the surface. Ca+Mg-HCO3 is formed from the dissolution of carbonate minerals, most likely from the Kalambaina limestone in the study area. Figure 4: Schoeller Plot showing level of contamination in the analysed water sample. The Gibbs plots (Figures 5a and b) were used to interpret and define the source of the chemical species in the analyzed groundwater samples. This plot demarcated three domains for the anions and cations, which are the precipitation, Rock, and Evaporation domains. The Ca Mg Na K Cl HCO3 NO3 Parameters 0.0 0.1 1.0 10.0 100.0 Co nc en tra tio n ( me q/l ) Schoeller Plot AAAAAA AAAAAA AAAAAA AAAAAA AAAAAA AAAAAA AAAAAA GGGGGG GGGGGG GGGGGG GGGGGG GGGGGG GGGGGG GGGGGG KKKKKK KKKKKK KKKKKK KKKKKK KKKKKK KKKKKK KKKKKK OOOOOO OOOOOO OOOOOO OOOOOO OOOOOO OOOOOO OOOOOO DDDDDD DDDDDD DDDDDD DDDDDD DDDDDD DDDDDD DDDDDD HHHHHH HHHHHH HHHHHH HHHHHH HHHHHH HHHHHH HHHHHH LLLLLL LLLLLL LLLLLL LLLLLL LLLLLL LLLLLL LLLLLL PPPPPP PPPPPP PPPPPP PPPPPP PPPPPP PPPPPP PPPPPP QQQQQQ QQQQQQ QQQQQQ QQQQQQ QQQQQQ QQQQQQ QQQQQQ RRRRRR RRRRRR RRRRRR RRRRRR RRRRRR RRRRRR RRRRRR SSSSSS SSSSSS SSSSSS SSSSSS SSSSSS SSSSSS SSSSSS EEEEEE EEEEEE EEEEEE EEEEEE EEEEEE EEEEEE EEEEEE TTTTTT TTTTTT TTTTTT TTTTTT TTTTTT TTTTTT TTTTTT UUUUUU UUUUUU UUUUUU UUUUUU UUUUUU UUUUUU UUUUUU WWWWWW WWWWWW WWWWWW WWWWWW WWWWWW WWWWWW WWWWWW XXXXXX XXXXXX XXXXXX XXXXXX XXXXXX XXXXXX XXXXXX IIIIII IIIIII IIIIII IIIIII IIIIII IIIIII IIIIII MMMMMM MMMMMM MMMMMM MMMMMM MMMMMM MMMMMM MMMMMM BBBBBB BBBBBB BBBBBB BBBBBB BBBBBB BBBBBB BBBBBB FFFFFF FFFFFF FFFFFF FFFFFF FFFFFF FFFFFF FFFFFF JJJJJJ JJJJJJ JJJJJJ JJJJJJ JJJJJJ JJJJJJ JJJJJJ NNNNNN NNNNNN NNNNNN NNNNNN NNNNNN NNNNNN NNNNNN CCCCCC CCCCCC CCCCCC CCCCCC CCCCCC CCCCCC CCCCCC LegendLegend A 1 E 2 I 3 M 4 B 5 F 6 J 7 N 8 C 9 G 10 K 11 O 12 D 13 H 14 L 15 P 16 Q 17 R 18 S 19 T 20 U 21 W 22 X 23 http://www.azojete.com.ng/ mailto:%20odumaoke@gmail.com Arid Zone Journal of Engineering, Technology and Environment, Dec, 2023; Vol. 19(4):793-806. ISSN 1596-2490; e-ISSN 2545-5818; www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 800 dominance origin for both cations and anions in the analyzed water sample is precipitation dominance, with a few samples falling in the precipitation domain and evaporation domain. Figure 5a and b: Controlling mechanisms for groundwater quality in the study area (after Gibbs, 1970). The Wilcox diagram (Figure 6) shows the level of salinity of water samples in the study area which is generally ranging from low to very high salinity hazard especially in samples 5 and 6. Figure 6: Wilcox diagramfor all the samples in the study area. file:///C:/user/Downloads/azojete143/www.azojete.com.ng mailto:%20odumaoke@gmail.com Abdulganiyu et al: Hydrochemistry of Surface and Groundwater in Parts of Birnin Kebbi Northwestern Nigeria. AZOJETE, 19(4):793- 806. ISSN 1596-2490; e-ISSN 2545-5818, www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 801 Table 4: Heavy metals measured in the surface and groundwater Sample Number Cr Fe Cu Pb Ni 1A BDL BDL BDL BDL 1.8001 1B -0.7450 -1.8240 0.2544 -0.1175 BDL 2A -0.2941 0.0147 0.2786 -0.1992 BDL 2B BDL BDL BDL BDL 1.6278 3B -0.3993 0.0624 0.3149 -0.1447 1.7722 4B 0.6376 0.1908 0.2871 -0.0448 1.7221 5A 0.7621 0.3156 0.2386 -0.1175 1.7555 6B 0.7256 0.3230 0.3137 -0.2173 0.1505 7 0.6333 0.3266 0.3246 -0.0312 BDL 8A 0.5775 0.3670 0.4191 0.4772 BDL 9B 0.6634 0.3817 0.6068 1.1445 BDL 10B 0.6720 0.4257 0.2701 -8.5337 BDL 11A 0.5839 0.4514 0.2737 -9.7639 0.3009 12A 2.6063 0.3450 0.3924 0.4137 0.4124 13B -0.1589 0.3413 0.3537 0.5771 0.5629 14B 0.3134 0.4074 0.3174 1.7256 0.5629 15B 0.3564 0.9322 0.3089 -45.2956 0.5517 16A 0.9489 1.5598 -0.2798 -18.7022 0.6075 17B 0.7492 0.7230 0.2968 -33.8270 -0.1672 18B 0.4487 -4.3455 0.2750 -45.1039 -0.0279 19B 0.4830 -2.8002 0.2750 -20.3727 0.0724 20B -0.4165 0.4367 0.3331 -45.2945 0.3009 21B 0.5088 -36.7001 0.2980 -29.5198 0.2285 22B 0.7729 -0.4844 0.3125 -45.2945 -0.3177 23 0.5925 -2.5066 0.3089 0.3637 0.3511 Average 0.459824 -1.81264 0.292957 -12.0451 0.7196 Table 5: Summary of physical parameters and heavy metals measured in the study area. The results of the heavy metals displayed in Table 4 reveal average values for cr2+ 0.459824, Fe2+-1.81264, Cu2+0.292957, Pb2+-12.0451, and Ni2+ 0.3009, respectively. These values were compared to the WHO (2011) standard in Table 5, which shows that all fall within the acceptable limit permissible for human consumption. Evaluated physical and chemical parameters revealed that water resources reveal the presence of Mg2+ which indicates the hardness of the water. This could be due to the presence of alkaline earth metals such as magnesium, which remarkably influence the chemistry of the water at the location. Ca2+ in twenty out of the twenty-three water analyzed samples comply with the WHO (2007) and NSDWQ (2007; 2015) standards, with the exception of samples from location 3B, which have 268 mg/l, while locations 12B and 16A have 286 mg/l, respectively. The presence of Ca2+ indicates the hardness of the water, which could be due to the presence of alkaline earth Parameter Minimum Maximum Mean Std. Deviation Variance Kurtosis WHO (2011) Cr -.7450 2.6063 .4409 .6371575 .406 4.904 50 Fe -36.7001 1.5598 -1.6423 7.4203392 55.061 23.262 300 Cu -.2798 .607 .2709 .1616117 .026 5.710 2000 Pb -45.2956 1.72 - 11.9151 17.7880 316.414 -.419 3000 Ni -.3177 1.80 .4907 .6785633 .460 -.069 70 EC 70.0000 9692.00 1317.37 74 2638.7740 6963128.2 56 7.506 1000 TDS 35.0000 5501.00 883.500 1 1705.7613 2909621.7 11 3.939 500 pH .270000 7.32 5.1821 2.14828 4.615 .697 6.5-8.5 TEMP 33.30000 34.20 33.8702 .2606 .068 -.394 30-32 http://www.azojete.com.ng/ mailto:%20odumaoke@gmail.com Arid Zone Journal of Engineering, Technology and Environment, Dec, 2023; Vol. 19(4):793-806. ISSN 1596-2490; e-ISSN 2545-5818; www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 802 metals such as calcium, which remarkably influence the chemistry of the water in the location. All the major oxides analyzed for all twenty-three samples fall within the WHO (2007) and NSDWQ (2007; 2015) standards except for HCO3 2-. The HCO3 2- for sixteen of the twenty- three samples is in tandem with the WHO (2007) and NSDWQ (2007; 2015) standards, except for samples from seven locations: 5B 124 (mg/l), 12B 104 (mg/l), 13A 112 (mg/l), 16A 136 (mg/l), and 18A 108.(mg/l), 19A 148 (mg/l), and 23 108 (mg/l), respectively. The high values of Ca2+, Mg2+ and HCO3 2- recorded in the samples could result from the breakdown and dissolution of carbonate rock, mainly limestone, which occurs in the study area. The contaminants may have migrated through tectonic and sedimentary structures, which serve as conduit pipes for rapid transmission to the groundwater system in the study area. Low-salinity Ca-Mg-HCO3 water is the most common type in the research area. Nemerow pollution index was used to evaluate the water quality of the study area. NPI value exceeding 1.0 indicate the presence of impurity in water and hence require some treatment before being used. Other interpretations of the Nemerow pollution index are shown in Table 6 while the result from Nemerow pollution index is displayed in Table 7. Table 6: Standard and classes of computed pollution used in this study Pollution Index Standard /Class Standard Source Nemerow Pollution Index (Npi) Ni< 1 No Pollution Adopted from Liu Et Al., (2015a) 1 ≤ 𝑁𝐼 < 2.5 Light Pollution 2.5 ≤ 𝑁𝐼 < 7 Moderate Pollution Ni ≥ 7 Heavy Pollution Table 7: Below is Nemerow’s pollution index for water quality showing the level of contamination in the water samples Nemerow's Pollution Index [Water Quality Index) NPI Values of Various Sampling Locations Parameters NSDWQ, 2015 Location 1 Location 2 Location 3 Location 4 Location 5 Location 6 PH 8.5 0.75 0.64 0.80 0.86 0.82 0.19 TDS 500 0.94 0.59 1.64 0.11 0.92 3.56 E.C 1000 0.94 0.59 1.64 0.11 0.92 3.56 Mg2+ 20 9.72 4.38 3.36 3.72 3.96 5.04 Na+ 200 0.03 0.02 0.10 0.00 0.04 0.02 Cr2+ 0.05 0.00 0.00 0.00 12.75 15.24 14.51 Fe2+ 0.3 0.00 0.05 0.21 0.64 1.05 1.08 Cu2+ 1 0.25 0.28 0.31 0.29 0.24 0.31 Ni 0.02 90.01 81.39 88.61 86.11 87.78 7.53 Pb2+ 0.01 0.00 0.00 0.00 0.00 0.00 0.00 Cl - 250 0.00 0.00 0.00 0.01 0.01 0.00 NO3 - 50 0.04 0.02 0.05 0.03 0.04 0.02 location 7 Location 8 Location 9 Location 10 Location 11 Location 12 Location 13 0.72 0.78 0.82 0.07 0.49 0.73 0.77 0.11 0.11 0.11 1.24 0.09 0.11 0.11 0.11 0.11 0.11 1.24 0.09 0.11 0.11 3.84 2.70 2.58 5.46 3.66 0.25 2.82 0.00 0.00 0.00 0.01 0.00 0.00 0.01 12.67 11.55 13.27 13.44 11.68 52.13 0.00 1.09 1.22 1.27 1.42 1.50 1.15 1.14 0.32 0.42 0.61 0.27 0.27 0.39 0.35 0.00 0.00 0.00 0.00 15.05 20.62 28.15 0.00 47.72 114.45 0.00 0.00 41.37 57.71 0.01 0.01 0.00 0.00 0.00 0.01 0.01 0.03 0.02 0.03 0.02 0.02 0.03 0.03 file:///C:/user/Downloads/azojete143/www.azojete.com.ng mailto:%20odumaoke@gmail.com Abdulganiyu et al: Hydrochemistry of Surface and Groundwater in Parts of Birnin Kebbi Northwestern Nigeria. AZOJETE, 19(4):793- 806. ISSN 1596-2490; e-ISSN 2545-5818, www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 803 Location 14 Location 15 Location 16 Location 17 Location 18 Location 19 Location 20 Location 21 Location 22 Location 23 0.75 0.80 0.03 0.64 0.61 0.10 0.41 0.64 0.65 0.72 0.09 0.11 11.00 0.43 0.19 9.69 0.07 0.31 0.13 0.09 0.09 0.11 1.51 0.42 0.19 9.69 0.07 0.31 0.13 0.09 2.58 3.90 6.78 6.30 3.90 5.04 3.12 3.66 3.12 3.90 0.00 0.01 0.04 0.02 0.01 0.01 0.00 0.01 0.01 0.00 6.27 7.13 18.98 14.98 8.97 9.66 0.00 10.18 15.46 11.85 1.36 3.11 5.20 2.41 0.00 0.00 1.46 0.00 0.00 0.00 0.32 0.31 0.00 0.30 0.28 0.28 0.33 0.30 0.31 0.31 28.15 27.59 30.38 0.00 0.00 3.62 15.05 11.43 0.00 17.56 172.56 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 36.37 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 0.01 0.00 0.02 0.04 0.02 0.03 0.03 0.04 0.03 0.02 0.07 0.06 Values > or = 1 indicates presence of pollution in the water sample However, the pH NPI value varies from 0.03 to 0.86 in all sampling stations that fall within the permissible NPI range. Table 6. The TDS NPI value varies, but all fall within the permissible limit except in sampling locations L3 = 1.64, L6 = 3.56, L10 = 1.24, L16 = 11.0, and L19 = 9.69, respectively. The EC NPI value falls within the permissible range except for L3 = 1.64, L6 = 3.56, L10 = 11.24, L16 = 1.51, and L19 = 9.69. The NPI value for Mg2+ for only sample L12 falls within the permissible limit, with others ranging from 2.58 to 9.72. The EC NPI value falls within the permissible range except for L3 = 1.64, L6 = 3.56, L10 = 11.24, L16 = 1.51, and L19 = 9.69. The NPI values for Na+ all fall within the permissible range. The Cr2+ value for L 1, L2, L3, and L13 all fall within the permissible range, but other samples range from 6.27 to 52.13, which fall outside the NPI range. The Fe2+ ranges L1, L2, L3, L4, L18, L19, L21, L22, and L23 all fall within the NPI range, but other sampling locations indicate a range of 1.05 to 5.20, which is unsuitable for drinking purposes. The Cu2+NPI for all samples is within the NPI range. The Ni NPI value for samples L7, L8, L9, L10, L17, L18, and L22 is within the NPI range, but others range from 7.53 to 90.01, making them unsuitable for drinking purposes. The values for Pb2+ all fall within the permissible NPI range except for L8, L9, L12, L13, L14, and L23, which indicate pollution. The Cl and NO3 - exhibit values below the NPI range of 1. 4.0 Conclusion The hydro-chemical study of the twenty-three water samples from drinking water sources in Birnin Kebbi Old Town and its environs was conducted to determine the pollution and contamination status. Results revealed surface and groundwater with concentrations of pH, Na2+, Cu2+, Cl- and NO3 - and higher concentrations of TDS and EC, which are above the NSDWQ (2015) set limits. The results also show that the cations Na2+ and Cu ions from the locations have values less than the maximum limit recommended by NSDWQ (2015), while Mg2+ and Fe2+ have higher values with lower values for trace elements like Cr2+, Ni, and Pb2+. Also, the anions analyzed, Cl- and NO3 - ion have concentrations within the limits of NSDWQ (2015) recommended for drinking water. The dominance of the Ca2+Mg2+-HCO3 facie over the other two types can be related to the geology and other geochemical processes that operate within the aquifers in the area. However, Application of Nemerow’s pollution index shows that the majority of the sampling locations displayed high NPI values, especially for Ni2+ and Pb2+. The NPI Ni2+ values for eleven (11) out of twenty-three samples, making up 47.83%, have NPI values that range from 7.53 to 90.01, making them unsuitable for drinking purposes. The NPI values for Pb2+ for six (6) samples, making up about 26.09%, have high NPI values that range from 36.37 to 172.56, depicting a high level of pollution. The Nemerow pollution index for evaluating the water quality, shows some pollutants have concentrations that are above standards. The people in the study area directly rely on the available surface and groundwater http://www.azojete.com.ng/ mailto:%20odumaoke@gmail.com Arid Zone Journal of Engineering, Technology and Environment, Dec, 2023; Vol. 19(4):793-806. ISSN 1596-2490; e-ISSN 2545-5818; www.azojete.com.ng Corresponding author’s e-mail address: charger.ca34@gmail.com 804 for drinking and domestic use from boreholes, river and open wells without any treatment. However, if the water is to be consumed for these purposes, proper treatment is necessary to avoid adding to the already existing health issues that affect not only older people but also children and younger people. 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