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MINISTRY OF EDUCATION AND TRAINING NHA TRANG UNIVERSITY OLUOWO ELOHOR FREEMAN EFFECTSOFTEMPERATUREONTHEENVIRONMENTALCONCENTRATIONSOFTRACE METALS: A CASE STUDY OFTHE OVWIAN MANGROVE, DELTA STATE, NIGERIA NORWEGIAN HIGHER EDUCATION DEPARTMENT (NORHED) MASTERS THESIS KHANH HOA – 2018 MINISTRY OF EDUCATION AND TRAINING NHA TRANG UNIVERSITY OLUOWO ELOHOR FREEMAN EFFECTSOFTEMPERATUREONTHEENVIRONMENTALCONCENTRATIONSOFTRACE METALS: A CASE STUDY OFTHE OVWIAN MANGROVE, DELTA STATE, NIGERIA NORHED MASTERS THESIS Major Topic allocation Decision Decision on establishing the Committees Defense date: Supervisor (s) (Full name): Prof Augustine Arukwe Chairman: (Full name) Faculty of Graduate Studies: (Full name) KHANH HOA - 2017 UNDERTAKING I undertake that the thesis entitled: “Effects ofTemperatureontheEnvironmentalConcentrationsofTrace Metals: A Case Study ofthe Ovwian Mangrove, Delta State, Nigeria” is my own work The work has not been presented elsewhere for assessment until the time this thesis is submitted … , Date …… month ……… year Elohor Freeman OLUOWO iii ACKNOWLEDGMENT I would like to seize this opportunity to acknowledge first, God Almighty for the privilege of life and the overall success ofthe program, and those who made my stay in Vietnam worthwhile to mention The Norhed Management Board and Course Lecturers, Graduate Studies Department, Nha Trang University and the Rectorate Board My gratitude will be incomplete without mentioning the likes of Prof Kim Anh Nyugen, Prof Claire Armstrong, Dr Ngan Nyugen, Prof Nghia Ngo Dang, Dr Pham Thi Thanh Thuy, Dr Duy Nguyen Ngoc, Ms Le Anh Han, my father and friend, Prof Curtis Jolly for his words of encouragement and Prof Karin Pittman, my academic mentor, for providing me numerable academic materials and support which has helped me to develop great academic skills To my supervisor, Prof Augustine Arukwe, for his uncommon scientific knowledge, amidst his busy schedule provided timely feedbacks, materials, correction to my thesis, making it a useful library and reference material I appreciate you sir To my lovely wife, Onome Destiny Elohor and beautiful daughters Divine and Marvelous Elohor Freeman for their understanding and support throughout the study period My parents, Chief Isaac John Oluowo for laying the foundation for my life and finally to all my course mate in the program, I love you all Thank you ………… , Date month Elohor Freeman OLUOWO iv year TABLE OF CONTENT UNDERTAKING iii ACKNOWLEDGMENT iv LIST OF ABBREVIATIONS .vii LIST OF SYMBOLS viii LIST OF TABLES ix LIST OF FIGURES x ABSTRACT xii CHAPTER ONE 1.0 Literature Review 1.1 Objective of Study 1.2 Heavy Metals in Aquatic Ecosystems 1.2.1 Toxicity of Heavy Metals 1.2.2 Some Heavy Metals and Their Sources 1.3.0 Description of Study Area and Sampling Stations 11 1.3.1 Geography 11 1.3.2 Geology 12 1.3.3 Climate 13 1.3.4 Vegetation and Land use 13 1.3.8 Human Activities 14 CHAPTER TWO 15 2.0 MATERIALS AND METHOD 15 2.1 Sampling Techniques 15 2.1.1Water and sediment 15 2.1.2 Water 15 2.1.3 Sediment 15 2.2.0 SAMPLING STATIONS 16 2.2.1 Sampling stations 16 2.3.0 WATER STUDIES 17 2.3.1 Rainfall 17 2.3.2 Temperature 17 2.3.3 Hydrogen Ion Concentration 17 2.3.4 Alkalinity 18 2.3.5 Total Hardness 18 2.3.6 Dissolved Oxygen 19 v 2.3.7 Conductivity 19 2.3.8 Total Solids 20 2.4.0 Pretreatment and digestion of water 20 2.4.1 For ICP scan 20 2.4.2 For AAS analysis 21 2.5.0 Bottom Sediment Studies 21 2.5.1 The Organic Matter 21 2.5.2 Pretreatment and digestion of sediment 21 2.5.3 For the AAS analysis 22 2.6.0 Instrumental Procedure 22 2.6.1 The Inductively Coupled Plasma Spectrometer (ICP) 22 2.6.2 The Atomic Absorption Spectrometer (AAS) 22 2.7 Data Analysis 23 CHAPTER THREE 24 3.1 RESULTS 24 3.1.1 Water Temperature 25 3.1.2 Hydrogen ion concentration (pH) 26 4.1.3 Total Alkalinity (mg/L) 27 3.1.4 Total Hardness of Water 27 3.1.5 Total Dissolved Solids (mg/L) 28 3.1.7 Biochemical Oxygen Demand (BOD) 29 3.2.0 HEAVY METAL CONCENTRATIONS 30 3.2.1 Copper (Cu) 30 CHAPTER FOUR 40 4.0 DISCUSSION 40 4.1 Physicochemical conditions of Ovwian Mangrove 40 4.2 Heavy metals in surface water and bottom sediment of Ovwian Mangrove 43 5.0 CONCLUSION 46 RECCOMMENDATION 47 References 48 vi LIST OF ABBREVIATIONS FEPA :Federal Environmental Protection Agency USEPA :United States Environmental Protection Agency DPR :Department of Petroleum Resources NIS :Nigerian Industrial Standards ATSDR :Agency for Toxic Substances and Disease Registry OSHA :Occupational Safety and Hazard Analysis ALAD :Aminolevulinate dehydratase HS :Heme Syntheses APHA :American Public Health Association NPA :National Population Commission DSC :Delta Steel Company GPS :Geographical Positioning System BOD :Biochemical Oxygen Demand TDS :Total Dissolved Solids DO :Dissolved Oxygen ASTM :American Society for Testing and Materials ICPMS :Inductively Coupled Plasma Mass Spectrometer AAS :Atomic Absorption Spectrometer SPSS :Statistical Package for the Social Sciences vii LIST OF SYMBOLS Mg/L: Milligram per litre Ppt: Parts per millions Ntu: Nephelometric Turbidity Units ºC: Celsius SE: Standard Error Cu: Copper Zn: Zinc Fe: Iron Cd: Cadmium Cr: Chromium Pb: Lead As: Arsenic viii LIST OF TABLES Table 4.1 Summary of some physico-chemical parameters of Ovwian Mangrove Table 4.2 - - - - 26 - 27 Summary of some heavy metals in Surface water in Ovwian Mangrove, Delta State, Nigeria - Table 4.3 - - Summary of some heavy metals in bottom sediment in Ovwian Mangrove, Delta State, Nigeria ix - - - 27 LIST OF FIGURES Fig 2.1 Map ofthe study area showing sampling stations Fig Spatial and monthly variation ofTemperature Fig 4.2 Spatial and monthly variation of PH Fig 4.3 Spatial and monthly variation of alkalinity Fig 4.4 Spatial and monthly variation of water hardness Fig.4.5 Spatial and monthly variation of Total Dissolved Solids (TDS) - 31 Fig 4.6 Spatial and monthly variation of Dissolved Oxygen (DO) - 32 Fig 4.7 Spatial and monthly variation of Biochemical Oxygen - 33 Fig 4.8 Spatial and monthly variation of Salinity - - - - - - - - - - 33 Fig 4.9 Spatial and monthly variation of Copper (Cu) in surface water - 35 Fig 4.10 Spatial and monthly variation of Copper (Cu) in bottom sediment - 35 Fig 4.11 Spatial and monthly variation of Zinc (Zn) in surface water - 37 Fig 4.12 Spatial and monthly variation of Zinc (Zn) in bottom sediment - 37 Fig 4.13 Spatial and monthly variation of Iron (Fe) in surface water Fig 4.14 Spatial and monthly variation of Iron (Fe) in bottom sediment Fig 4.15 Spatial and monthly variation of Cadmium (Cd) in surface water Fig 4.16 Spatial and monthly variation of Cadmium (Cd) in bottom sediment - 41 Fig 4.17 Spatial and monthly variation of Chromium (Cr) in surface water Fig 4.18 Spatial and monthly variation of Chromium (Cr) in bottom sediment -43 Fig 4.19 Spatial and monthly variation of Lead (Pb) in surface water Fig 4.20 Spatial and monthly variation of Lead (Pb) in bottom sediment - Fig 21 Spatial and monthly variation of Arsenic (As) in surface water - - 47 Demand (BOD) - - - x - - - - - - - - 14 - 28 - 29 - - 30 - - 31 - - - 39 - 39 - 41 - 43 - - 45 45 Metals in Bottom Sediment Stati on Stati on Stati on Mea n SD S.Er ror MINMAX 0.42 Stat ion 0.21 1.32 0.37 0.11 0.25 0.22 0.13 0.85 0.98 0.41 1.13 0.10 0.21 1.08 0.56 1667 0.28 4667 0.60 9167 0.48 1456 0.10 4531 0.46 6512 0.19 6554 0.04 2674 0.19 0453 0.210.335 0.1350.413 0.1191.083 6.00 4.15 5.39 4.08 5.68 3.86 7.48 9.50 9.43 7.10 7.83 8.24 4.10 5.32 9.13 5.74 6.70 4333 7.36 4167 5.50 7667 1.94 9523 2.06 5938 1.34 6088 0.79 5889 0.84 3416 0.54 9538 4.0829.508 4.1549.432 3.8637.102 206 241 582 228 917 0.00 0.00 0.01 290 350 238 320 225 432 001 125 073 0.01 0.01 0.00 406 021 256 043 0.01 0.03 0.00 362 401 300 752 0.02 0.00 0.00 395 01 375 123 0.00 0.01 0.00 267 011 216 502 0.00 0.00 0.00 271 5167 350 671 250 4017 0.01 0.01 0.00 5833 57.3 0342 78.3 3408 84.1 9079 0.00 5621 0.01 004 0.00 392 23.3 9402 31.9 7975 34.3 7075 0.00 2295 0.00 4099 0.00 16 206.1350.0 241.582395.01 125.073375.123 0.0060.014 0.0060.032 0.0010.011 2.03 0.98 1.05 0.95 2.03 2.54 1.89 0.93 0.83 1.11 0.85 2.02 0.89 1.83 1.38 2.20 1.82 0.78 1.43 95 1.59 1.32 2833 0.58 2609 0.65 4339 0.58 0821 0.23 7849 0.26 7133 0.23 7119 0.8502.034 0.8322.546 0.7812.201 Lead 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 25 0.00 4667 0.00 0.00 2811 0.00 4179 0.00 0.00 1147 0.00 1706 0.00 0816 0.0010.008 0.010.003 0.0010.006 Arsen ic 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1167 0.00 0 0-0.001 0.00 0408 0.00 0167 0-0.001 Copp er Zinc Iron Cadm ium Chro mium Augu st Septe mber Octo ber Stat ion 0.33 0.32 0.23 Stati on 7.53 6.84 0-0.001 Copper Anova: Two-Factor Without Replication SUMMARY SW.1 SW.2 SW.3 SW.4 SW.5 SW.6 BS.1 BS.2 BS.3 BS.4 BS.5 BS.6 Count 3 3 3 3 3 3 August September October Sum 0.003 0.006 0.004 0.012 0.004 0.008 0.896 0.912 0.687 2.308 2.533 1.397 Average 0.001 0.002 0.001333 0.004 0.001333 0.002667 0.298667 0.304 0.229 0.769333 0.844333 0.465667 Variance 0.000001 3.3333E-07 0.000007 3.3333E-07 2.3333E-06 0.00288233 0.026221 0.000427 0.35630633 0.14546533 0.28885033 12 3.384 0.282 0.19068927 12 1.724 0.143667 0.02665624 12 3.662 0.305167 0.19974197 ANOVA Source of Variation Rows Columns Error SS 3.130656 0.18302 1.457306 Total 4.770983 df MS F 11 0.284605 4.29649632 0.09151 1.38146815 22 0.066241 P-value 0.0017703 0.272161031 35 Zinc Anova: Two-Factor With Replication SUMMARY SW.1 Count Sum Average Variance Stand.Error BS.1 August 0.076 0.01266 0.00012 0.00458 Septembe r 0.09 0.015 6.92E-05 0.003396 October 0.041 0.00683 9.77E06 0.00127 Total 18 0.207 0.0115 7.28529E05 F crit 2.258518357 3.443356779 Count Sum 40.226 6.70433 3.80064 0.79588 4.268102 0.843416 33.046 5.50766 1.81195 0.54953 12 40.302 3.3585 13.9399 12 44.275 3.689583 12 33.087 2.75725 16.67015 9.07612 df Interaction SS 381.876 5.36145 5.26672 Within 49.4045 30 MS 381.876 2.68072 2.63336 1.64681 Total 441.909 35 Average Variance Stand.Error Total Count Sum Average Variance ANOVA Source of Variation Sample Columns 44.185 7.364167 2 18 117.457 6.52538888 3.53126131 F 231.887817 1.62782313 1.5990627 Iron Anova: Two-Factor With Replication SUMMARY SW.1 Count Sum Average Variance Standard Error BS.1 Count Sum Average Variance Standard Error Total Count August September October Total 0.067 0.011167 6.34E-05 0.00325 6 18 0.045 0.025 0.137 0.0075 0.004167 0.007611 5.5E-06 1.14E-05 3.23E-05 0.000957 0.001376 1629.11 271.5183 3283.496 23.39336 6 18 2104.206 1502.41 5235.726 350.701 250.4017 290.8737 6140.218 7088.089 6830.032 31.99015 34.37075 12 12 12 P-value 1.1736E15 0.2132249 0.2188343 F crit 4.17087 3.31583 3.31583 Sum Average Variance 1629.177 135.7648 21596.9 ANOVA Source of Variation Sample Columns Interaction Within SS 761427.6 16776.15 16775.38 82559.01 Total 877538.1 2104.251 1502.435 175.3543 125.2029 36332.63 20321.56 df 2 30 MS F P-value F crit 761427.6 276.6848 1.08915E-16 4.170876786 8388.074 3.048028 0.062362335 3.315829501 8387.691 3.047889 0.06236956 3.315829501 2751.967 35 Cadmium Anova: Two-Factor With Replication SUMMARY August September October Total SW.1 Count Sum Average Variance Standard Error BS.1 Count Sum Average Variance Standard Error Total Count Sum Average Variance ANOVA Source of Variation Sample Columns Interaction 6 0.013 0.008 0.002166667 0.001333333 5.76667E-06 6.66667E-07 0.000980363 0.000333333 0.006 0.001 0 18 0.027 0.0015 2.14706E-06 0.084 0.014 0.0001008 0.00409878 0.035 0.005833333 1.53667E-05 0.001600347 18 0.215 0.011944444 6.01732E-05 12 12 0.109 0.092 0.009083333 0.007666667 6.33561E-05 8.98788E-05 12 0.041 0.003416667 1.33561E-05 SS 0.000981778 0.000208722 0.000143722 MS 0.000981778 0.000104361 7.18611E-05 0.096 0.016 1.88E-05 0.001770122 df 2 F 41.65959453 4.428335691 3.049269213 P-valu 3.94401 0.02064 0.06229 Within Total 0.000707 30 0.002041222 35 2.35667E-05 Chromium Anova: Two-Factor With Replication Septembe SUMMARY August r October Total SW.1 Count 6 18 Sum 0.013 0.01 0.006 0.029 0.00216666 0.00161111 Average 0.001667 0.001 5.76667E2.36928EVariance 06 1.47E-06 06 0.00098036 Standard Error 0.000494 BS.1 Count 6 18 Sum 9.537 9.594 7.937 27.068 1.3228333 1.50377777 Average 1.5895 1.599 0.3373533 0.44498630 Variance 0.6884527 0.42816 0.33873605 Standard Error 0.267133 0.2371193 Total Count 12 12 12 Sum 9.55 9.604 7.943 0.79583333 0.6619166 Average 0.800333 1.00010669 0.6298633 Variance 0.890475 ANOVA Source of Variation Sample Columns SS 20.3085422 0.14845238 df Interaction 0.1464905 Within 7.2698645 30 27.8733496 35 Total MS 20.308542 0.0742261 0.0732452 0.2423288 F P-value 83.8057253 3.434E-10 0.30630362 0.738438 0.30225563 0.741373 F crit 4.17087 3.31583 3.31583 Lead Anova: Two-Factor With Replication SUMMARY August September October Total SW.1 Count 6 18 Sum 0.006 0.007 0.006 0.019 0.0011666 0.00105555 Average 0.001 0.001 1.6667E5.55556EVariance 07 08 0.0001666 Standard Error BS.1 Count 6 18 Sum 0.015 0.009 0.015 0.039 0.00216666 Average 0.0025 0.0015 0.0025 4.02941EVariance 7.9E-06 0.0000007 4.3E-06 06 0.00114 0.0003415 0.00084 Standard Error 7 Total Count 12 12 12 Sum 0.021 0.016 0.021 0.0013333 Average 0.00175 0.00175 4.2424E2.57EVariance 4.2E-06 07 06 ANOVA Source of Variation Within SS 1.11E05 1.39E06 2.72E06 6.53E05 Total 8.06E05 Sample Columns Interaction df 2 30 MS 1.11E05 6.94E07 1.36E06 2.18E06 F 5.10204081 0.31887755 0.625 35 Arsenic Anova: Two-Factor With Replication Augus SUMMARY t SW.1 Septembe r Octobe r Total P-value 0.03132 0.72939 0.54208 F crit 4.17087 3.31583 3.31583 Count Sum Average Variance Standard Error BS.1 Count Sum 0.006 0.001 0 0.006 0.001 0 0.006 0.001 0 18 0.018 0.001 1.99E-37 0.006 0.007 0.006 Average Variance Standard Error Total Count Sum Average 0.001 0 0.001167 1.67E-07 0.000167 0.001 0 18 0.019 0.00105 5.56E-08 12 0.012 0.001 5.13E38 12 0.013 0.001083 12 0.012 0.001 5.13E38 df Within SS 2.78E08 5.56E08 5.56E08 8.33E07 Total 9.72E07 Variance ANOVA Source of Variation Sample Columns Interaction 8.33E-08 2 30 35 MS 2.78E08 2.78E08 2.78E08 2.78E08 F 1 P-value 0.32530 0.37981 0.37981 F crit 4.17087678 3.31582950 3.31582950 ... undertake that the thesis entitled: Effects of Temperature on the Environmental Concentrations of Trace Metals: A Case Study of the Ovwian Mangrove, Delta State, Nigeria” is my own work The work has...MINISTRY OF EDUCATION AND TRAINING NHA TRANG UNIVERSITY OLUOWO ELOHOR FREEMAN EFFECTS OF TEMPERATURE ON THE ENVIRONMENTAL CONCENTRATIONS OF TRACE METALS: A CASE STUDY OF THE OVWIAN MANGROVE,... Conductivity Electrical conductivity of water is a numerical expression of the ability of an aqueous solution to conduct electric current This ability is a function of the presence of ions, their