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Cadmium and lead adsorption capacity of selected nsukka urban soils

 

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  • Title Page                                                                                                                                             iApproval Page                                                                                                                                                 iiCertification                                                                                                                                        iiiDeclaration                                                                                                                                         ivDedication                                                                                                                                           vAcknowledgements                                                                                                                           viList of Figures                                                                                                                                     viiList of Tables                                                                                                                                     xList of Abbreviations                                                                                                                         xiTable of Contents                                                                                                                             xiiAbstract                                                                                                                                          xviiiCHAPTER ONE1.0       INTRODUCTION                                                                                                                 1Background of the Study   1Behaviour of Metals in Soils   2Statement of the Problem   4 4 Aim and Objectives of the Study                                                                                               41.
  • 4.1  Aim of study                                                                                                                             41.
  • 4.2  Objectives of Study                                                                                                                 5Significance of the Study                                                                                                       5Scope of Study                                                                                                                     6 CHAPTER TWO2.0       LITERATURE REVIEW                                                                                                    
  • 72.1    Adsorption Phenomena                                                                                                             72.
  • 1.1  Physical adsorption (Physisorption)                                                                                           82.
  • 1.2  Chemical adsorption (Chemisorption)                                                                                      
  • 82.2     Sorption in Soils                                                                                                                      
  • 92.3      Surface Complexation                                                                                                                        
  • 92.4      Parameters influencing adsorption of heavy metals on soils                                                 122.
  • 4.1  Soil pH                                                                                                                                     122.
  • 4.2  Soil organic matter                                                                                                                   122.
  • 4.3  Metal ion                                                                                                                                 132.
  • 4.4  Soil type                                                                                                                                 132.4.
  • 4.1Oxides in soils                                                                                                                       142.4.
  • 4.2Surface functional groups in soils                                                                                          
  • 142.5      Individual Adsorption Behavior of Cadmium (Cd) and Lead (Pb)                                     152.
  • 5.1    Cadmium                                                                                                                               152.
  • 5.2    Lead                                                                                                                                      
  • 162.6       Adsorption Isotherm                                                                                                            
  • 172.7      Empirical Models                                                                                                                   182.
  • 7.1    Linear Adsorption (Kd Approach) Isotherm                                                                         182.
  • 7.2    Freundlich Isotherm                                                                                                               192.
  • 7.3    Langmuir Isotherm                                                                                                              
  • 202.8      Sorption Kinetics                                                                                                                   202.
  • 8.1    Lagergren Pseudo- first order kinetics model                                                                       212.
  • 8.2  Pseudo- second order kinetics model                                                                                     212.
  • 8.3  Intra-particle diffusion model                                                                                              
  • 222.9     Review of Some Previous Works Done on Adsorption of Metals by Soils                           23CHAPTER THREE3.0       EXPERIMENTALS                                                                                                                        
  • 303.1      Description of study area                                                                                                      
  • 303.2      Location of the sample points in the study area                                                                    
  • 313.2      Collection of Samples                                                                                                            
  • 333.3      Materials Used                                                                                                                       333.
  • 3.1  Reagents                                                                                                                                 333.
  • 3.2  Equipment                                                                                                                              
  • 373.4      Sample Preparation and Analysis                                                                                           393.
  • 4.1  Preparation of Stock Solution of the Metal Ions                                                                   393.
  • 4.2  Preparation of 1000 mg/L of Pb(NO3)2 Stock Solution                                                         393.
  • 4.3   Preparation of Diluted Solution of Pb(NO3)2 from Stock Solution                                     393.
  • 4.4  Preparation of 1000 mg/L of Cd(NO3)2 Stock Solution                                                         403.
  • 4.5   Preparation of Dilute Solution of Cd(NO3)2 from Stock Solution                                         403.
  • 4.6   Preparation of
  • 0.01M CaCl2                                                                                                 413.
  • 4.7    Preparation of
  • 0.05M NaOH                                                                                                           413.
  • 4.8    Preparation of
  • 0.10M NaOH                                                                                                           423.
  • 4.9    Preparation of
  • 0.10M KCl                                                                                                   423.4.
  • 1.0  Preparation of 1 M K2Cr2O7                                                                                                 423.4.
  • 1.1 Preparation of 1 M FeSO4                                                                                                     423.4.
  • 1.2 Preparation of
  • 0.01M EDTA                                                                                                           433.4.
  • 1.3 Preparation of
  • 0.05M HCl                                                                                                   433.4.
  • 1.4 Preparation of 20 % KOH Solution                                                                                       433.4.
  • 1.5 Preparation of 1 % Phenolphthalein                                                                                     433.4.
  • 1.6 Preparation of 1 % Diphenylamine Indicator                                                                       433.4.
  • 1.7 Preparation of 1 N CH3COONH4                                                                                         443.4.
  • 1.8 Preparation of
  • 0.10M Potassium Hydrogen Phathalate                                                       443.4.
  • 1.9 Preparation of
  • 0.10M Potassium Dihydrogen Phosphate                                                     443.4.
  • 2.0Preparation of Ammonium Hydroxide Buffer 10 Solution                                                   443.4.
  • 2.1Preparation of pH Buffer 4 Solution                                                                                     443.4.
  • 2.2 Preparation of pH Buffer 7 Solution                                                                                    
  • 453.5      Treatment of Soil Samples for Determination of Cadmium and Lead Concentration          
  • 453.6      Determination of Physico-Chemical Properties of the Soil Samples                                     453.
  • 6.1  Determination of particle size distribution                                                                             453.
  • 6.2  pH Determination                                                                                                                   473.
  • 6.3  Determination of carbon content                                                                                           483.
  • 6.4  Determination of organic matter                                                                                             483.
  • 6.5  Determination of cation exchange capacity (CEC)                                                               493.
  • 6.6  Determination of exchangeable acidity (EA = Al3+, H+)                                                       493.6.
  • 6.1Determination of exchangeable aluminium (Al3+)                                                                 503.6.
  • 6.2Determination of exchangeable hydrogen ion (H+)                                                               513.6.
  • 7.0Determination of exchangeable bases (EB = Ca2+ and Mg2+)                                               513.6.
  • 7.1Determination of calcium ion (Ca2+)                                                                                       513.6.
  • 7.2Determination of magnesium ion (Mg2+)                                                                               523.
  • 6.8  Determination of sodium and potassium ion (Na+ and K+)                                                   523.
  • 6.9  Adsorption studies using batch equilibrium technique                                                           523.6.
  • 9.1Determination of the effect of pH on adsorption                                                                   533.6.
  • 9.2Determination of the effect of contact time on adsorption                                                   543.6.
  • 9.3Determination of the effect of initial metal ion concentration on adsorption                                   543.6.
  • 9.4Determination of the effect of temperature on adsorption                                                    
  • 553.7      Adsorption studies data analysis                                                                                           55CHAPTER FOUR4.0       RESULTS AND DISCUSSION                                                                                         
  • 564.1      Results of Concentration of Cadmium and Lead in Soil Samples                                         56
  • 4.2Results of Physico-Chemical Parameters of Soil Samples                                                           584.
  • 2.1  Results of effect of pH on adsorption of Pb2+ and Cd2+                                                       604.
  • 2.2  Results of effect of temperature on adsorption of Pb2+ and Cd2+                                         634.
  • 2.3  Results of effect of initial metal ion concentration on adsorption     of Pb2+ and Cd2+       664.
  • 2.4  Results of effect of contact time on adsorption of Pb2+ and Cd2+                                        
  • 694.3      Results of adsorption isotherms                                                                                             724.
  • 3.1  Langmuir isotherm model                                                                                                       724.
  • 3.2  Freundlich isotherm model                                                                                                     814.
  • 3.3  Temkins isotherm model                                                                                                        
  • 884.4      Results of adsorption kinetics                                                                                               954.
  • 4.1  Pseudo-first order kinetics                                                                                                     954.
  • 4.2  Pseudo-second order kinetics                                                                                                         1024.
  • 4.3  Weber and morris intra-particle diffusion kinetics                                                               109 CHAPTER FIVE5.0       CONCLUSIONS                                                                                                               
  • 1165.1      Conclusions                                                                                                                           116REFERENCES                                                                                                                               118APPENDIX                                                                                                                                     126  

Thesis Abstract

The presence of heavy metals in the environment constitutes a potential source of both soil and groundwater pollution which is a major environmental concern worldwide. The retention of cadmium and lead by selected Nsukka urban soils obtained from three different sampling locations with a range of soil properties representing the ultisol soil type of tropics was investigated. The effects of contact time, pH, concentration, and temperature on the adsorption process were investigated using the batch technique equilibrated for 24 hours at room temperature. For all soils examined, the study revealed that the adsorption capacities of the soils for cadmium (Cd) and lead (Pb) increased with increase in pH, temperature, contact time, and concentration. The adsorption data were fitted to the Langmuir, Freundlich and Temkins adsorption isotherm. The results indicated that the adsorption isotherm could be satisfactorily described by the Langmuir model. On the basis of the maximum adsorption capacity (qmax), the order of affinity of cadmium and lead for the studied soils was Pb2+ > Cd2+. The maximum adsorption values for Pb range from 2.06 to 2.54 mg/g while that for Cd range from 1.02 to 1.34 mg/g. Three simplified kinetic models including pseudo-first order, pseudo-second order and Weber and Morris intra-particle diffusion were used to fit the experimental data. The kinetic data of the adsorption process for Pb2+ and Cd2+ in all soils studied gave better satisfactory fit to pseudo-second order model compared to the Weber and Morris intra-particle diffusion and pseudo-first order, respectively.

 

 


Thesis Overview

<p> </p><ul><li><strong>INTRODUCTION</strong></li><li><strong>Background of the Study</strong></li></ul><p>Soil is one of the most important components of all terrestrial ecosystems and is of essential importance and it plays a pivotal role in the sustenance of all life forms on the planet. Some of the roles played by soil range from the simplest of functions like providing anchorage and nutrients for the growth of crops, trees and grassland, and regulating water supplies, to more complex functions such as helping in maintaining a clean environment via degradation and transfer of biomass and being a source and sink for atmospheric gases1. The importance of soils to all life forms cannot be overemphasize.</p><p>Soil is a very complex heterogeneous mixture, which consists of solid phases (the soil matrix) containing minerals and organic matter and fluid phase (the soil water and the soil air), which react with each other and ions entering the soil system2.</p><p>Due to growing industrialization and urbanization, heavy metals are increasingly introduced into the environment mainly soil, via a variety of sources. These sources include industrial processes, application of sewage sludges, fertilizers, pesticides, and fungicidal sprays applied to plants, atmospheric deposition, municipal effluent, and disposal of electronic waste.3 Unfortunately, some of these heavy metals can be taken up by crops, thereby entering the food chain. Hence, soils provide a potential pathway with which heavy metals may become bioavailable to humans.</p><p>Soils in urban environment have direct influence on public health, this is because they receive higher than normal loads of contaminants from anthropogenic activities, mostly in industrial areas. Most of the heavy metals are bound to particles in sediments, but only a small quantity becomes dissolved in the water and it can spread widely in the food chain4.</p><p>The term heavy metal refers to any metallic element that has a relatively high density, toxic or poisonous at low concentrations, that are stable and cannot be degraded or eliminated5. Heavy metals have been classified into essential and non-essential metals. The essential metals are needed by living organisms in trace quantities for optimum performance of life processes. They include Ni, Fe, Zn, Co, Mo, e.t.c.6. Insufficient supply of these essential metals in an organism, leads to problems associated with growth and ability to complete its life cycle, while sufficient supply results in optimum conditions &nbsp; and excess supply results in toxic effects and possibly death7.</p><p>The non-essential elements include As, Ag, Cd, Hg, and Pb and the ability of various organisms to accommodate these non-essential metals are limited8. They may be tolerated at very low concentrations, some are toxic even if their concentration is very low, and their toxicity increases with accumulation in water and soils9.</p><p>Heavy metal ions are the most toxic inorganic pollutants which are present in soils and can be of natural or anthropogenic origin10. Heavy metals may be found in soils11, ground water12, sediments, plants13 and even in dust14. They cause many health problems, some of which include cancer, renal damage, Wilson’s disease(neurological or psychiatric symptoms of liver disease, compounded with heavy metal deposits), lung damage, dermatitis, nausea, chronic asthma, headache, dizziness, rapid respiration, e.t.c.12, 15.</p><ul><li><strong>Behaviour of Metals in Soils</strong></li></ul><p>The soil is the primary recipient either by design or accident of diverse waste products and chemicals used in industry16. Natural source of trace metal elements in soils is parent materials of the soil. Anthropogenic sources, including industrial emissions and effluents, bio-solids, fertilizers, and pesticides can also contribute to the increase in the amount of heavy metals in soils17. Heavy metals are spread to the ground in several ways, such as spillage or corrosion of products that contain heavy metals. The heavy metals that are spread to the ground by airborne particles remain mainly in the ground where they are deposited, because heavy metals have strong affinity for the soil matrix17. In the ground, heavy metals are distributed as either soluble in the soil solution, sorbed to the soil matrix or precipitated as solids17. While in the soil solution, heavy metal can exist as a free ion, as well as soluble complexes with different organic and inorganic ligands17. Common inorganic ligands in the soil are SO42-, Cl¯, OH¯, PO43-, NO3¯ and CO32-, and common organic ligands are low molecular weight aliphatic, aromatics, amino acids and soluble constituents of fulvic acids such as phenol17.</p><p>The persistence of heavy metals in the soil and its reduction in mobility involves the phenomena of sorption, desorption, precipitation, complexation, oxidation/reduction and dissolution. Although these phenomenons can occur simultaneously, adsorption mechanisms are known to be determinant in the control of metal availability and solubility in the soil18. Adsorption phenomenon in soils controls the concentration of metal ions and complexes in the soil solution and thus can exert a major influence on translocation of the metal ions in plant19.</p><p>The term ‘sorption’ is often broadly used to encompass all processes that involve either the retention or release of contaminants in soil. Sorption process is one of the most important chemical processes that occurs in soils, it governs the rate and quantity of nutrient uptake by plants, transport of heavy metals, radionuclides, pesticides, organic pollutants and other materials within soil systems. Sorption processes are complex and are influenced by soil properties such as texture, bulk density, pH, organic matter, cation exchange capacity, and the type and amount of the different clay minerals present in any particular soils20.</p><p>Adsorption of heavy metals in soil involves two mechanisms. One is selective adsorption, in which surface complexes are formed; while the other is non-selective adsorption, in which the metallic cations act as counter-ions in the diffuse layer. The importance of each of these mechanisms depends on the metal and the nature of soil21.</p><p>Contamination of the environment most especially soils, by heavy metals, through increasing anthropogenic activities, has been on the rise in recent years and this has been of considerable concern due to environmental hazards, and various health problems it poses such as cancer, gene mutation, neurological disorder, e.t.c. Moreover, since soils offer a possible sink for pollutants, there is a need to investigate how pollutants are sorbed by soil and the fate of the pollutants in the environment. Furthermore, the presence of heavy metals in Nsukka urban soil has been well documented by researchers22, 23.However, the adsorption capacity of the soil for heavy metals has not been reported. Also, reports on how Nigerian soils function as sorbent for heavy metals are limited in literature. In addition, IUPAC observed that the majority of investigations of fate of pollutants in the environment have been conducted in temperate soils, predominately in Europe and North America, with limited report on tropic soils most especially Africa24. However, approximately one-half of the earth’s population and roughly one-third of its land mass are found in the tropics24. Hence, this has necessitated and underscores the need for this study.</p><ul><li><strong>Aims and Objectives of the Study</strong></li></ul><p><strong>1.4.1 &nbsp; Aims of Study</strong></p><p>The main aim of the present work is to study the retention capacity of cadmium (Cd) and lead (Pb) by selected Nsukka urban soils as well as to investigate the effect of some parameters on the adsorption of Cd and Pb by the soils using the batch technique.</p><p><strong>&nbsp;</strong></p><p><strong>&nbsp;</strong></p><p><strong>&nbsp;</strong></p><p><strong>&nbsp;</strong></p><p><strong>&nbsp;</strong></p><p><strong>1.4.2 &nbsp; Objectives of Study</strong></p><p><strong>&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; </strong>The objectives of this research work are to:</p><ol><li>ascertain the physico-chemical properties of soil of the study area.</li><li>determine cadmium and lead adsorption capacity of Nsukka urban soils by investigating</li></ol><p>the effects of pH, concentration, temperature and contact time on the adsorption process.</p><p>iii. evaluate the adsorption isotherm of the adsorption process using the empirical models; &nbsp; Langmuir, Freundlich and Temkin isotherm.</p><ol><li>propose the mechanism of the adsorption process using kinetics models of pseudo-first order, pseudo-second order and Weber and Morris intra-particle diffusion.</li><li>provide baseline data on cadmium and lead adsorption capacity of the soils of the study areas.</li></ol><p><strong>1.5 &nbsp; &nbsp; Significance of the Study</strong></p><p>This study is of a great significance to the researcher as the knowledge created in relation to the study will be of immense benefit towards the understanding of how cadmium and lead are sorbed by the soil and the bioavailability of these metal ions in soil of the study areas. Additionally, the knowledge created regarding the study can give a clue on cadmium and lead translocation in plants grown on the soils.</p><p>Also, the outcome of this study can be of help towards contributing to the design of effective remediation strategies and providing possible alternatives for a preventive environmental control that is needed by environmentalist via formulation of guidelines.</p><p>Furthermore, the outcome of the study can serve as additional database to the researchers in onward adsorption studies of heavy metals by soils, most especially tropical soils.</p><p><strong>&nbsp;</strong></p><p><strong>&nbsp;</strong></p><p><strong>1.6 &nbsp; &nbsp; &nbsp; Scope of Study</strong></p><p>The research focuses on and is limited to cadmium and lead adsorption capacity of Nsukka urban soils using batch equilibrium techniques. The investigation was done by varying operational variables such as pH, initial concentration, contact time, and temperature to determine the effects of the variables on the adsorption process. The adsorption capacity of the soils for the metal ions is described using empirical models; Langmuir, Freundlich and Temkins adsorption isotherm model. The mechanism of the reaction is described using the pseudo-first order, pseudo-second order and Weber and Morris intra-particle diffusion kinetics model.</p> <br><p></p>

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