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Impact of Mining and Agriculture on Metal Concentrations in Soil and Food Crops in Selected Local Government Areas of N Asarawa State, Nigeria

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Impact of Mining and Agriculture on Metal Concentrations in Soil and Food Crops in Selected Local Government Areas of N Asarawa State, Nigeria Impact of Mining and Agriculture on Metal Concentrations in Soil and Food Crops in Selected Local Government Areas of N asarawa State, Nigeria. By Okere John Uchechukwu RegNo. 03552001 Being a Thesis Submitted to the Postgraduate School In Partial fulfillment of the Requiren1ents for the award of the Degree of Doctor of Philosophy (Ph.D) In Analytical Chemistry in the Department of Chemistry, Faculty of Science, University of Ahuja, Ahuja, Nigeria July, 2008 CERTIFICATION We certify that this research work was carried out by OKERE, JOHN ONYEMAUCHEKUKWU Reg. No. 03552001 for the award of Doctor of Philosophy (Ph.D) in Analytical Chemistry in the Department of Chemistry, University of Abuja. Prof. T.A. Arowolo Date External Examiner ......27 /...L·/l� '!. /.............. ·· Date Prof. S.E. I(akulu·········· (Supervisor)� 6 :?)tit.� ........................... ••••••••••• jog < ?---J1r Dr. C.D. Chup Date (Internal Examiner) ......... )�............. ... r.'9..I.� .1. 7 ............ Dr. H.D. Aliyu Date Head of Department ��·············· Prof. N . ........,..., ............ Dean, Postgraduate School 11 DEDICATION This work is dedicated first, to God Almighty, who gives wisdom, knowledge and understanding liberally to them that ask from Him; and to my family (wife and children); Dorothy Okere, Ifeoma Okere, Chukuwdinma Okere, Chukwuemeka Okere; to my late elder brother whose wish and encouragement was that I obtain a Doctoral degree in Chemistry. Ill I l.l..; ACKNOWLEDGEMENTS Th is work was made possible during hectic and trying experimental times by my Professor and Supervisor Samuel E. Kakulu, whose advice and guidance helped produce a good research write- up with worthy experience. Also, my gratitude goes to my fa mily; Dorothy Okere, Ifeoma Okere, Chukwudinma Okere, Chukwuuemeka Okere whose encouragement and assistance saw me through 3 years of intensive academic and research work. My regards also goes to my nephew Kelechi Okere who assisted me in computer processing of words, data and charts. I will not forget the contribution of Mr. Richard Mmegwa, Mr. Monday Irene, Mr. Chris Uwadiale, Ms Sarah Joseph and other members of Chemistry Department, University of Abuja, whose conh·ibution in no small measure, helped in the completion of all laboratory work. Finally, my greatest thanks and appreciation goes to God who through divine inspirations provided me with sound arguments in support of most of the research findings, explanations and discussions. John Uchechukwu Okere July, 2008. iv ABSTRACT The total concentration of Cd, Co, Cu, Mn, Ni, Pb and Zn were detemlined in the soil and plant materials from some selected local government areas of Nassarawa state, Nigeria. The modified USEPA- 3050 me thod of HNOr HCI04 - H202 was used in the preparation of soil sample fo r total deternlination whilst the plant materials were digested with HN03 -H 202. The CaCh. DTPA extraction method was used in the determination of the concentration of bio available metals in soil samples. The flame atomic absorption spectrometry was used in the de te rmination of metals in the soil and plant digests. A precision of 8.5, 6.1, 4.5, 3.1, 2.4, 1.2, and 2.5, percents were obtained fo r Zn, M,n, Cd, Cu, Co, Pb and Ni respectively, for soil samples; whilst plant sample materials gave precisions of 4.2, 3.2, 4.5, 3.3, 1.7, 2.9 and 3.2 percents respectively, for Zn, Mn, Cd, Cu, Co, Pb and Ni. Quality assurance of the digestion me thod for trace metal determination in soil was carried out by a recovery study and the analysis of Certified Re ference Material (CRM); SD- M 2/TM ; Pacific Ocean soil sediment sample (1990). Percent re coveries of 89- 96% were obtain for most metals. The range of metals (mgkg- 1) in the re ference soil materials were 71.8 - 76, 1165- 1200, 27.0 -37. 9, 0.09 -0. 15, 12.8- 14.1, 21.4 24.6 and 49.5 - 57.2 for Zn, Mn, Cu, Cd, Co, Pb and Ni respectively and these were in agreeme nt with the Certified Values as show by the student t- te st.The soils were slightly ac idic with the pH ranging from 5.9 - 6.7 in study are a and the percent organic carbon varied from 1.20 -1.53% The total metal levels in the soils (mkkg- 1) v varied from 15.0 - 84.0, 160.0- 342.0, 41.0-76.0, 1.0-2.83, 0.1-0.4, 4.10-9.16 and 13.0 -39.0 for Zn, Mn, Cu, Cd, Co, Pb and Ni, respectively. The percent bio available metals in the soil ranged from 11-15, 10 -15, 15 -20, 7- 10, 5-10, 5- 10 and 2-4, fo r Zn, Mn, Cd, Co and Ni respectively, in (mgkg-1) The concentration of metals in plant material (mgkg-1) we re 1. 18 -9.3 (4. 13) fo r Zn; 6.4 -40. 0(18.25) for Mn; 0.1-0.7 (0.24) for Cd;l.8-6.8 (3 .78) fo r Cu; 0.10-0.98 (0.42) fo r Ni . Pb; 0.1-0.80 (0.36) and 0.01- 0.03 (0.02) fo r Co. Generally, mining and agticultural activities were suspected to be the major contributors of metals in the study area. The average concentrations of Zn, Mn, Cu, Cd, Co, Pb and Ni obtained in the study area fo r soil and food crops were compared with other regional studies, country standards and quality guidelines to evaluate their risk significance and quality assessments specified fo r the protection of human health. These levels compared favourably with results fi:om other regional studies, country standards, as well WHO/FAO benchmarks fo r soil and fo od quality standards . That the concentrations of metals in this study were lower than quality guidelines for agriculture, residential and commercial purposes indicate that there is currently no threat to human health in the use of the soil and consumption of fo od crops in these areas. r VI TABLE OF CONTENTS CHAPTER ONE Page 1.0 �ODUCTION 1 1.1 General Introduction 1-2 1.2 Heavy metals 2-3 1.3 Sources of Heavy Metals 3 1.3.1. Natural Sources 3-4 1.3.2 Anthropogenic Sources 7 1.3.2.1 Agricultural Chemicals 7 1.3.2.2 Mining 9 1.3.2.3 Industrial Emissions 10 1.3.2.4 Chemical Industry 11 1.4 Soil and plants as Indicators of heavy metal Pollution of the environment 12-1 1.4.1 Soils 12 1.4.2 Plants 15-16 1.5 Fate and Mobility of heavy metals in soil 19-20 1.6 Plant uptake of heavy metals in soil 20-21 1.7 Metal uptake and toxicity in animals 21-23 1.8 Significance of Some Heavy Metals to Plants and Animals 24 Zinc 24 Cadmium 24 Nickel 25 Manganese 26 Lead 26 Copper 26 Cobalt 27 1.9 Aim of study 27 -29 VII CHAPTER TWO 30 2.0 LITERATURE REVIEW ON HEAVY METAL DETERMINATION SOIL AND PLANTS 30 IN 2.1 Sampling and Sample Preservation 30 2.1.1 Soils 31-33 2.1.2 Plants 33-35 2.2 Sample Preparation methods 35 2.2.1 Digestion of soil samples 36-39 2.2.2. Determination of total metals in soil 39-41 2.2.3 Sequential Extraction 41-44 2.3 Plant sample determination 45 2.3.1. Wet Ashing or wet-digestion 45-46 2.3.2 Dry Ashing 46- 48 2.4 Analytical techniques fo r metal determination in soils and plant materials 48 2.4.1 Atomic Absorption Spectrophotometer (AAS ) 48 2.4.2 A typical published application of AAS 48 2.4.3 Atomic Fluorescence Spectrophotometer (AFS) 49 2.4.5 Neutron Activation Analysis (NAA) 49-50 2.4.6 X-ray Fluorescence (XRF) 50 CHAPTER THREE 51 3.0 EXPERIMENTAL 51 3.1 Study Area 51 3.2 Sample collection and preservation 51 3.2.1. Soil sample collection, preparation and preservation 56 3.2.2 Plant sample collection, preparation and preservation 56-57 3.3 Chemicals and reagents 58 3.4 Cleaning of glassware 58 3.5 Preparation of standard stock solutions of metals 59-60 3.6 Working Standard stock solutions of metals 60 3.7. Instrumentation 60 VIII 3.7.1 Atomic Absorption Spectrophotometer 60 3.7.2. pH meter 61 3.8 Digestion of soil samples for total metal determination 61 3.8.1 Recovery Studies 61 3.8 Extraction of soil sample for soluble metal determination 62 3.9 Digestion of plant (food crop) samples for metal determination 62-63 3.11. Reference sample material analysis 63 3.12. Determination of organic carbon of soil 63-64 3.13 Determination of soil pH 64 CHAPTER FOUR 65 4.0 RESULTS 65 4.1 Quality Assurance of Method 65 4.2 Total Metals in Soil 66 4.2.1 pH, Cd and Cu 67-68 4.2.2 Cobalt, Manganese and Nickel 68-69 4.2.3 Lead and Zinc 69-70 4.2.4 Percent Organic Carbon (O.C) in soil 74-75 4.2.5 Bio-Available Metal in Soil 75 4.3 Metals in Vegetation and Food Crops 76 4.3.1 Cadmium and Copper 76-77 4.3.2 Cobalt, Manganesse and Nickel 77 4.3.3 Lead and Zinc 78 CHAPTER FIVE 82 5.0 Discussion and Conclusion 82 5. 1 Variations of Metals in Soil, bio-Available Metal in Soil and Metals in Plants 82 5.1.1 Variation of Metal in Soil 82-84 5.1.2 Variation of Bio-Available Metal in Soils 84-86 5.1.3 Variation of Metals in Plants (Food Crops) and Its Implication In Diet and and Human Consumption 86-88 IX 5.2 pH and % organic carbon 88-89 5.3 Health Implications of Some Metals (Cu, Cd and pH) found in Study Area Above WHO FAO acceptable foods 89-91 I hrnits m 5.4 Relationship Bio-Available Metals inSoil with Levels in Plants 91-93 5.5 Correlation Study 96 5.5.1 Conelations between metals in Soils (dry seasn) 101 5.5.2 Conelations Between Metals in Soil (Rainy Season) 102 5.5.3 Correlation Between Soil pH and Soil Metals in the Sh1dy Area 102 5.5.4 Correlation Between Soil (O.C) and Soil Metal (Rainy Season)103 5.5.6 Correlation Between Soil pH and Soil Organic Carbon for all Locations 104 5.6 Factors of Accumulations of Heavy Metals in Soils 104-106 5.7 Comparism of Metals in Soil of Study Area with Other Regional Study 108-109 5.8 Comparism ofMetals in Soil ofSh1dy Area With Soil Quality Criteria for Different Countries 109-110 5.9 Comparism of Heavy Metal in Food Crops/Plant in Study Area with Other Regional Studies and WHO Standards 111-114 5.10 Conclusion
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