ASSESSMENT OF HEAVY METAL STATUS AROUND MAJOR INDUSTRIAL SITES IN SOUTHERN CROSS RIVER STATE, NIGERIA USING ATOMIC ABSORPTION SPECTROPHOTOMETER (AAS) METHOD

International Journal of Advanced Scientific and Technical Research ISSN 2249-9954 Available online on http://www.rspublication.com/ijst/index.html volume 15, No. 5, 2025 DOI: 10.5281/zenodo.17342174 Original Article ©2025 RS Publication, rspublicatio[email protected] 354 ASSESSMENT OF HEAVY METAL STATUS AROUND MAJOR INDUSTRIAL SITES IN SOUTHERN CROSS RIVER STATE, NIGERIA USING ATOMIC ABSORPTION SPECTROPHOTOMETER (AAS) METHOD EFFIONG, E. J. 1 , PAUL, E. E. 2 and AKPAITAM, M. S. 3 1. Department of Science Technology, Akwa Ibom State Polytechnic, Ikot Osurua, Akwa Ibom State, Nigeria, 2347067831405, [email protected] 2. Department of Science Technology, Foundation Polytechnic, Ikot Idem, Akwa Ibom State, Nigeria, 2347066628508, [email protected] 3. Department of Science Technology, Akwa Ibom State Polytechnic, Ikot Osurua, Akwa Ibom State, Nigeria, 2348136286173, [email protected] ARTICLE INFO ABSTRACT ©2025 RS Publication Paper ID: IJASTR68E9FC7A298F9 Received: 2025-09-13 Published: 2025-10-13 DOI: https://dx.doi.org/1 0.5281/zenodo.173421 74 Page No: 354-369 This research focuses on assessment of heavy metal concentration in the soils of industrial areas in Southern Cross River State. Soil samples in the immediate vicinity of some selected industrial sites at 15cm deep were collected in five sample locations of Southern Cross River state which include, Gitto Company, Zenith construction Ltd. Faith Plant, and UNICEM. This was done to evaluate the status of heavy metals (Fe, Cd, Co, Cu, Pd, Cr, Zn, Ni & Mn) present. The soil samples were subjected to a total digestion technique using HNO3 and HClO4 acids and analyzed using Atomic Absorption Spectrophotometer for the metals stated above. The metal concentration in ppm in all the site ranges from l63.35ppm – 2262ppm for Fe, 18.80ppm – 33.25ppm for Cd, 3.53ppm – 4.48ppm for Co, 21.40ppm – 38.10ppm for Cu, 22.55ppm for Pb, 6.10ppm – 15.12 ppm for Cr, 9.50ppm – 44.35ppm for Zn, 5.40ppm – 46.30ppm for Ni and 10.43ppm – 64.20ppm for Mn. The concentration of the various heavy metals showed a wide range of variation with variable pattern in the order Fe>>Mn>Ni>Zn>Cu>Cd>Pd>Cr>Co in the entire sample area. Significant enrichments were obtained for Cd, Cu, and Zn respectively at Unicem, but Pb was not significantly enriched in any sample location. The contamination index in this study ranged from uncontaminated (0) to moderately contaminated (1-2). The concentration of heavy metals in this study falls below the regulatory standard of other countries apart from Cd, an element associated with quarry and mining activities, waste batteries, and metal finishing industrial waste having concentration above the regulatory level of other countries. Keywords: Heavy metals, soil, quarry activities, industries, contamination. International Journal of Advanced Scientific and Technical Research Available online on http://www.rspublication.com/ijst/index.html ISSN 2249-9954 Cite This Paper: EFFIONG, ENOBONG J. PAUL, EDITI E. AND AKPAITAM, MFONISO S. (2025). "ASSESSMENT OF HEAVY METAL STATUS AROUND MAJOR INDUSTRIAL SITES IN SOUTHERN CROSS RIVER STATE, NIGERIA USING ATOMIC ABSORPTION SPECTROPHOTOMETER (AAS) METHOD". INTERNATIONAL JOURNAL OF ADVANCED SCIENTIFIC AND TECHNICAL RESEARCH (IJASTR), vol. 15, no. 5, 2025, pp. 354-369. DOI: https://dx.doi.org/10.5281/zenodo.17342174 International Journal of Advanced Scientific and Technical Research ISSN 2249-9954 Available online on http://www.rspublication.com/ijst/index.html volume 15, No. 5, 2025 DOI: 10.5281/zenodo.17342174 Original Article ©2025 RS Publication, rspublicatio[email protected] 355 INTRODUCTION Nigeria, being a developing country in the world today, is also a part of the industrialization process (Njoku et al., 2013) and economic development. Industrial pollution is one of the causes of environmental hazards and will continue to be a vital cause of natural pollution. Rapid urbanization and industrialization releases enormous volume of heavy metals into our environment. Soils is recognized as a major sink (Adriana, 2003) for anthropogenic heavy metals deposition through various pathway. Heavy metals are defined as metallic element that have a high relative density compared to water (Tchounnou et al, 2012). Heavy metals is among one of the pollution which causes several threats to human and the environment (Cheng, 2003). And it is becoming more serious with urbanization, industrialization and modern agricultural activities. Heavy metals does not easily degrade or volatilized owing to their stable physical and chemical properties (Singh et al.,2010, Adel et al., 2012) therefore it has led to more serious and possibly irreversible pollution resulting from increasing heavy metal accumulation in soil every year (Zhang et al., 2012). Due to this hazard posed by heavy metal in the soil determination is necessary as an indicator showing anthropogenic input in the environment. A quarry is an open pit mine from which rocks or rock minerals are excavated through various process that may comprise removal of the topsoil, drilling, blasting with explosive and use of machinery to crush and grade rock materials and for transportation. Quarry as every mining operation is a destructive activity whose sociology economic benefits may be unable to compensate for the soil overall detrimental effects on natural ecosystem (Ayodele, et al.,2014). International Journal of Advanced Scientific and Technical Research ISSN 2249-9954 Available online on http://www.rspublication.com/ijst/index.html volume 15, No. 5, 2025 DOI: 10.5281/zenodo.17342174 Original Article ©2025 RS Publication, rspublicatio[email protected] 356 This study is aimed at determining the heavy metal content in soils of in the major industrial sites in Southern Cross River State which includes quarries and stone crushing facility. MATERIALS AND METHOD. Surface soils of 15cm deep were collected using soil auger from each of the sampling site. The exact location for all sample sites was determined using global positioning system and entered into a geographical information system for data processing. Fig 1 shows the sample sites. The collected soil samples were air dried under laboratory condition for three days and drives through a 2.00mm mesh wire (Ismail, 1993). Samples of 1g was weighed and digested with HNO3 and HCLO4 in the ratio 3:1 heated in a fume cupboard. The digested sample was filtered using No 1 Whatman filter and the filtrate was made up to 50ml with distilled water. Then taken for heavy metal analysis by AAS (Isang et al., 2023). The concentration of Fe, Cd, Co, Cu, Pb, Cr, Zn, Ni, and Mn in the filtrate were determined using a flame atomic spectrophotometer using air acetylene flame with deuterium background correction. The light source, hallow cathode lamps were operated at the following analytical lines for each element: 252.3nm for Fe. 228.8nm for Cd, 327.4nm for Cu, 241.2nm for Co, 283.3nm for Pb, 359.4nm for Cr, 307.6nm for Zn, 231.1nm for Ni, and 280.1nm for Mn. After every determination, blanks and certified reference materials were also run to determine the precision and instrumental uncertainty. DATA ANALYSIS The environmental impact of metals and the pollution level in the end samples can be determined with the help of two parameters: (1) The enrichment factor (EF) and (2) geoaccumulation index (Igeo). The enrichment factor (EF) due to its universal formula is a relatively simple and easy tool for International Journal of Advanced Scientific and Technical Research ISSN 2249-9954 Available online on http://www.rspublication.com/ijst/index.html volume 15, No. 5, 2025 DOI: 10.5281/zenodo.17342174 Original Article ©2025 RS Publication, rspublicatio[email protected] 357 assessing the enrichment degree and comparing the contamination of different environmental media (Benhaddya and Hadjel, 2013) EF is used to determine the enrichment degree and comparing the contamination of different environmental media (Nowrouzi and Pourkhabbaz, 2014). Among the elements used to normalised the metal constituent for normalization have been Al. Fe and Sc. Fig 1 Map of Southern senatorial district of Cross River State showing sampling sites. The constituents chosen for this purpose should according to Nworouzi (2014) should not be altered. Therefore, for the purpose of this study, Fe was the metal used for normalisation because International Journal of Advanced Scientific and Technical Research ISSN 2249-9954 Available online on http://www.rspublication.com/ijst/index.html volume 15, No. 5, 2025 DOI: 10.5281/zenodo.17342174 Original Article ©2025 RS Publication, rspublicatio[email protected] 358  its anthropogenic source is small compare to natural source. The formula for EF is expressed in equation 1 below.  () = (  ) 1 (  ) Where EF (X) = enrichment factor for metal X, (X/Fe) SAMPLE = ratio of concentration of metal X to normalised elements (Fe) in the sample. (X/Fe) CONTROL = ratio of concentration of metal X to normalised elements (Fe) in a reference material such as the control sample Sutherland (2000) Contamination categories recognized on the basis of the enrichment factors are: EF< 1 No enrichment EF < 2 depletion to minimal enrichment, EF = 2-5 moderate enrichment, EF = 5-20 significant enrichment, EF = 20-40 very high enrichment, EF >40 extremely high enrichment Enrichment factor can be used to differentiate the metal originality from anthropogenic activities and those from natural procedures and to assess the degree of anthropogenic influence. When EF=1, then the elements are mainly derived from the crust or soul. When a certain element of EF was significantly greater than 1 and the average crustal components can show the contrast, the elements have been enriched. Geo-accumulation index (Igeo) was to assess the extent of Pb, Cd, Cr, Cu, Co, Mn, Ni, Zn, and Fe pollution of the soil samples in the study area. Geo-accumulation index (Igeo) was first used by International Journal of Advanced Scientific and Technical Research ISSN 2249-9954 Available online on http://www.rspublication.com/ijst/index.html volume 15, No. 5, 2025 DOI: 10.5281/zenodo.17342174 Original Article ©2025 RS Publication, rspublicatio[email protected] 359 Muller in 1969 as a tool that provides the extent of pollution of soil with regards to the background concentration of the polluted metal. Igeo formula is expressed in equation 2 below. Igeo =log 2   2 (.∗ )  The factor 1.5 is introduced to minimize the effect of possible variations in the background values, Cm background which may be attributed to lithogenic variations in soils. The background values here is the control. RESULTS The results of the topsoil samples within the sampling area of the major industries in Southern Cross River as presented in table 1 while the concentration of element in the control experiment is presented in table 2. TABLE 1: Concentration of elements (ppm) in different sample locations Location Fe Cd Co Cu Pb Cr Zn Ni Mn Gitto 1800.01 31.60 N.D 21.40 N.D 11.53 23.90 46.30 39.80 Zenith 1672.50 33.25 3.53 28.20 N.D 15.12 28.10 23.35 64.20 Faith plant 2262.00 19.80 4.48 38.10 22.55 13.31 44.35 22.10 56.20 Unicem 163.35 18.80 4.31 35.75 N.D 6.10 9.50 5.40 10.43 N.D. stands for not detected. International Journal of Advanced Scientific and Technical Research ISSN 2249-9954 Available online on http://www.rspublication.com/ijst/index.html volume 15, No. 5, 2025 DOI: 10.5281/zenodo.17342174 Original Article ©2025 RS Publication, rspublicatio[email protected] 360 Table 2: Concentration of elements in the control experiment Element Fe Cd Co Mo Cu Pb Cr Zn Mn Ni Concentration(ppm) 870.50 9.25 5.30 ND 11.05 4.20 7.24 18.32 14.01 7.72 Table 3: Enrichment factor. LOCATIONS Cd Co Cu Pb Cr Zn Ni Mn GITO 1.635 ND 1.505 ND 1.098 1.358 2.853 1.373 ZENITH 1.876 0.346 1.329 ND 1.019 1.729 1.570 2.384 FAITH PLANT 0.825 0.326 1.327 2.068 0.663 2.017 1.101 1.543 UNICEM 10.814 4.336 17.241 ND 4.480 5.942 3.727 3.967 Table 4: Geoaccumulation index ELEMENTS LOCATIONS Fe Cd Co Cu Pb Cr Zn Ni Mn Gitto 0.46 1.19 ND 0.37 ND 0.09 0.90 2.00 0.92 Zenith 0.36 1.26 -1.17 0.77 ND 0.48 1.14 1.01 1.16 Faith Plant 0.79 0.51 -0.83 1.20 1.83 0.29 1.79 0.93 1.42 UNICEM -3.00 -0.66 -0-88 -0.83 ND -0.83 -0.43 -1.10 -1.01 International Journal of Advanced Scientific and Technical Research ISSN 2249-9954 Available online on http://www.rspublication.com/ijst/index.html volume 15, No. 5, 2025 DOI: 10.5281/zenodo.17342174 Original Article ©2025 RS Publication, rspublicatio[email protected] 361 Fig 2: cluster bar of geoaccumulation index. Fig 3: 3.D surface presentation of geoaccumulation index geoaccumulation index UNICEM FAITH PLANT ZENITH GITTO - 4 - 3 - 2 - 1 0 1 2 3 Mn Ni Zn Cr Pb Cu Co Cd Fe geoaccumulation index Mn 2 Zn Ni 1 0 -1 -2 - 3 Pb Cr Cu Co Cd Fe - 3 -- 2 - 2 -- 1 - 1 - 0 0 - 1 1 - 2 International Journal of Advanced Scientific and Technical Research ISSN 2249-9954 Available online on http://www.rspublication.com/ijst/index.html volume 15, No. 5, 2025 DOI: 10.5281/zenodo.17342174 Original Article ©2025 RS Publication, rspublicatio[email protected] 362 DISCUSSION Level of Heavy Metal in Top Soil The concentration of Fe, Cd, Co, Cu, Pb, Cr, Zn, Ni and Mn in the topsoil sample within the 15cm depth from the study area were presented in table 1. the co centration of the various metals showed a wide range of variation with variable patterns in the order: Fe>Mn>Zn>Cu>Cd>Pb>Cr>Co. this pattern of heavy metal distribution is similar to the reports of Sultana et al., (2012), and Zabir et al., (2016), the concentration (ppm) of heavy metals in the soils samples ranges between 163.35ppm -2262.00ppm for Fe, 18.80ppm – 33.25ppm for Cd, 3.53ppm – 4.48ppm for Co, 9.30ppm – 38.10ppm for Cu, ND22.55ppm for Pb, 6.10ppm – 15.12ppm for Cr. 9.50ppm – 44.35ppm for Zn, 5.40ppm – 46.30ppm for Ni and 10.43ppm – 64.20ppm for Mn. According to Nirmal et al., (2007) and Kabir et al.,(2012), the concentration of zinc in this study is below safe limit. As compared to the regulatory levels for soil concentration established between different countries as reported by Kabir et al., (2012). Only cadmium is above safe limit. It is also found that heavy metals detected in this study is less than detected in a research carried out by Kodom et al., (2012) in soil heavy metal pollution in an industrial zone of Kumasi Ghana using XFR. The highest concentration of heavy metal in this study is Fe and cobalt is the least. Enrichment Factor. Table 3 above shows the enrichment factor of the analysed elements in all the sample locations, cadmium with 1.652 and 1.870 respectively at Gitto and Zenith had depletion to minimal enrichment implying that the elements are mainly derived from crust or soil while Unicem with EF of 10.81 showed significant enrichment. Cobalt with EF of 0.346 and 0.325 at Zenith and Faith Plant respectively had no enrichment while Unicem has moderate enrichment of 4.337. International Journal of Advanced Scientific and Technical Research ISSN 2249-9954 Available online on http://www.rspublication.com/ijst/index.html volume 15, No. 5, 2025 DOI: 10.5281/zenodo.17342174 Original Article ©2025 RS Publication, rspublicatio[email protected] 369 Sutherland, R. A. (2000). Bed Sediment Associated With Trace Metals in An Urban Stream, Oahu Hawaii. Journal of Environmental Geology, 39, 611 – 637. Syed, S. (2006)A Green Technology For Recovery Of Gold From Non-Metallic Secondary Sources, Hydrometallurgy82:48 - 53 Tchounwou, P.B, Yedjou, C. G, Patlolla, A. K. &Sulton, D. J (2012) Heavy Metal Toxicity and the Environment.Exs 101: 133 – 164 Usman.U. A, Kumar, P.,Abdulkadir A.B. Kamale H.I., Sadiq, H.M., Muhammed, D.D., Ibrahim, Y and Wulo, I.B. (2016)Geochemical assessment of toxic metals stocking in top-soil within the area of limestone quarry in Gombe of North-eastern Nigeria.African Journal of Environmental Science and Technology 10(9), 283-291. World Health Organisation (WHO) (1994). Quality Directive of Potable Water (2 nd ed.). Geneva: World Health Organisation, 197 – 198 Zabir .A.A, Zzaman, M.W.U, Hossen, M .Z, Uddin, M.N, Islam, M.S, & Islam, MS (2016). Spatial Dissemination Of Some Heavy In Soil Adjacent To Bhaluka Industrial Area, Mymensingh, Bangladish. American Journal of Applied Scientific Research. 2 (6), 38– 47.