K. VIJAYARAGHAVAN

BIOSORPTION OF METALS: A COMPLETE HANDBOOK

with 21 Figures, 16 Tables & 646 References

Vinanie Publishers

AuthorK. VijayaraghavanDepartment of Chemical EngineeringIndian Institute of Technology MadrasChennai 600036IndiaTel: (91)-(044)-22575156Fax: (91)-(044)-22570509E. mail: cevijay@iitm.ac.in; erkvijay@yahoo.com

ISBN: 978-81-932494-0-6

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iiiBiosorption of metals: A complete handbook

TABLE OF CONTENTS

Preface .........................................................................................viiAcknowledgements ..................................................................... ixList of symbols ............................................................................. xiList of abbreviations ................................................................. xv

1. Introduction ............................................................................. 1Metals and their classification 1.1 .......................................... 2

2. Current scenario in metal remediation technologies .... 9Physico-chemical methods 2.1 ................................................. 9Biological treatment methods 2.2 ......................................... 11

Bioprecipitation 2.2.1 ......................................................... 11 Bioaccumulation 2.2.2 ....................................................... 12Phytoremediation 2.2.3 ...................................................... 14

Rhizofiltration 2.2.3.1 ...................................................... 14Phytoextraction 2.2.3.2 .................................................... 16Phytostabilization 2.2.3.3 ................................................ 16Phytovolatilization 2.2.3.4 ............................................... 17Biosorption 2.2.4 .............................................................. 18

3. Types of biosorbents ............................................................. 23Bacterial biosorption 3.1 ....................................................... 23

Bacillus biomass 3.1.1 ........................................................ 26Pseudomonas biomass 3.1.2 .............................................. 30Corynebacterium biomass 3.1.3 ........................................ 31Streptomyces biomass 3.1.4 ............................................... 32Other bacterial biomasses 3.1.5 ........................................ 32

Fungal biosorption 3.2 ........................................................... 34Rhizopus biomass 3.2.1 ...................................................... 34Aspergillus biomass 3.2.2 .................................................. 36Penicillium biomass 3.2.3 .................................................. 37Yeast biomass 3.2.4 ............................................................ 37Macrofungi biomass 3.2.5 .................................................. 40Other fungal biomasses 3.2.6 ............................................ 41

Biosorption of metals: A complete handbook iv

Algal biosorption 3.3 .............................................................. 42Microalgae 3.3.1 ................................................................. 44Macroalgae 3.3.2 ................................................................ 45

Brown algal biomass 3.3.2.1 ............................................ 46Sargassum biomass 3.3.2.1.1 ..................................... 51Ascophyllum biomass 3.3.2.1.2 ................................... 53Turbinaria biomass 3.3.2.1.3 ..................................... 54Laminaria biomass 3.3.2.1.4 ...................................... 54Other brown algal biomasses 3.3.2.1.5 ...................... 55

Green algal biomass 3.3.2.2 ............................................ 56Red algal biomass 3.3.2.3 ................................................ 57

Biosorption by industrial wastes 3.4 .................................... 58Activated sludge 3.4.1 ........................................................ 58Chitinous materials 3.4.2 .................................................. 60Animal bones 3.4.3 ............................................................. 62Other industrial sorbents 3.4.4 ......................................... 65

Biosorption by agricultural wastes 3.5 ................................. 65Coir pith 3.5.1 ..................................................................... 66Rice husk 3.5.2 ................................................................... 66Sawdust 3.5.3 ..................................................................... 69Other agricultural wastes 3.5.4 ........................................ 69

4. Mechanism of metal removal by biosorption .................. 71Biosorption mechanisms 4.1.................................................. 71Understanding biosorption mechanisms through various techniques 4.2 ........................................................................ 75

Potentiometric titration 4.2.1 ............................................ 76FTIR spectroscopy 4.2.2 ..................................................... 77Scanning electron microscopy 4.2.3 .................................. 80Energy dispersive X-ray spectroscopy 4.2.4 ...................... 81X-ray Photoelectron Spectroscopy 4.2.5 ............................ 83Surface Area Analysis 4.2.6 ............................................... 83

5. Preparation of biosorbents for metal removal ............... 85Chemically modified biosorbents 5.1 .................................... 85Genetically modified biosorbents 5.2 .................................... 87Immobilized biosorbents 5.3 ................................................. 89

6. Batch biosorption .................................................................. 93Factors influencing batch biosorption 6.1 ............................. 93

vBiosorption of metals: A complete handbook

Biosorption isotherms 6.2.................................................... 100Batch experimental data modelling 6.3.............................. 103

Empirical modelling 6.3.1 ................................................ 103Langmuir model 6.3.1.1 ................................................. 104Freundlich model 6.3.1.2 ............................................... 104Jovanovic model 6.3.1.3 ................................................. 105Temkin model 6.3.1.4 .................................................... 105Dubinin-Radushkevich model 6.3.1.5 ........................... 105Flory-Huggins isotherm model 6.3.1.6 ......................... 106Elovich isotherm model 6.3.1.7 ..................................... 106Fowler-Guggenheim isotherm model 6.3.1.8 ................ 106Kiselev isotherm model 6.3.1.9 ..................................... 107Halsey isotherm model 6.3.1.10 .................................... 107Hill-de Boer isotherm model 6.3.1.11 ........................... 107Harkins-Jura isotherm model 6.3.1.12 ......................... 108Redlich-Peterson model 6.3.1.13 ................................... 108Sips model 6.3.1.14 ........................................................ 108Toth model 6.3.1.15 ........................................................ 109Khan model 6.3.1.16 ...................................................... 109Radke-Prausnitz isotherm model 6.3.1.17 .................... 109Fritz-Schlunder three parameter model 6.3.1.18 ......... 110Hill isotherm model 6.3.1.19 ......................................... 111Koble-Corrigan model 6.3.1.20 ...................................... 111Liu isotherm model 6.3.1.21 .......................................... 111Jossens model 6.3.1.22 .................................................. 112Weber-van Viletmodel 6.3.1.23 ...................................... 112Baudu model 6.3.1.24 .................................................... 112Fritz-Schlunder five parameter model 6.3.1.25............ 112

Error functions 6.3.2 ........................................................ 113Problems associated with linearization of non-linear mod-els 6.3.3 ............................................................................ 113Thermodynamic modelling 6.3.4 .................................... 114Mechanistic modelling 6.3.5 ........................................... 115

Batch kinetic studies 6.4 .................................................... 117Pseudo-first order model 6.4.1 ........................................ 118Pseudo-second order model 6.4.2 .................................... 119Elovich model 6.4.3 .......................................................... 119

Desorption and regeneration 6.5 ........................................ 120Multi-component systems 6.6 ............................................. 125

Multi-component modelling 6.6.1 ................................ 128

Biosorption of metals: A complete handbook vi

Extended Langmuir isotherm model 6.6.1.1 ............... 128Multi-component Freundlich isotherm model 6.6.1.2..129Multi-component Redlich-Peterson model 6.6.1.3 ....... 129Other multi-component models 6.6.1.4 ........................ 130

7. Continuous biosorption ..................................................... 133Biosorption using packed columns 7.1 ................................ 134Packed column regeneration 7.2 ......................................... 138Modelling of packed column data 7.3 .................................. 142

8. Scale-up of the biosorption process to industrial applica-tions ............................................................................................ 145

Behaviour of biosorbent in real solutions 8.1 ..................... 145Applicability of biosorption to industrial wastewater treat-ment processes 8.2 ............................................................... 152Process costs and overall scheme of biosorption 8.3 .......... 153Developing practical biosorbent to suit real applications 8.4 .................................................................... 154

9. Possible application of biosorption in other areas ..... 159

10. Scope and future directions ........................................... 163

References ................................................................................. 165

Index ........................................................................................... 201

viiBiosorption of metals: A complete handbook

PREFACE

The concept of adsorption is well known over a century. How-ever, only recently the potential of biological materials to adsorb various ions/molecules even in their inactive/dead form have been identified. This process of adsorption termed “biosorption” has at-tracted several researchers to invest their time and skill. As a re-sult of this, several biosorbents of different genera were identified as potent biosorbents for various metals, dyes and other organic pollutants. Being environmental-friendly as well as cost-effective, biosorption has several advantages over conventional adsorbent such as activated carbon. However, it should be emphasized that biosorption is still mostly lab-restricted technology and seldom ap-plied for real wastewater treatment. Several factors hindered the application of biosorption to industrial wastewaters and this book, in addition to fundamentals, also aims to specify the constraints of biosorption and procedure to eradicate these limitations in real applications. Thus, this book is basically designed to provide (i) an up-to-date look at on-going experimental as well as theoretical ac-tivities in the field of biosorption; (ii) critical investigation to clear the prevalent misunderstandings and errors; and (iii) suggestion to transform the available knowledge into applications.

Chapter 1 introduces the readers to metals and their im-pact on environment as well as living beings.

Chapter 2 reviews conventional as well as recent tech-niques to treat metal-bearing wastewaters. Biological treatment methods such as bioprecipitation, bioaccumulation and phytore-mediation (rhizofiltration, phytoextraction, phytostabilization and phytovolatilization) are discussed in detail with adequate literatures. Biosorption technique is introduced and its inherent advantages over other biological as well as conventional treatment methods are highlighted.

Chapter 3 summarizes performance of biosorbents to-wards various metal ions. The biosorbents taken into account in this chapter encompass various bacteria, fungi, micro-algae, mac-ro-algae, industrial and agricultural wastes.

Biosorption of metals: A complete handbook viii

Chapter 4 discusses metal removal mechanism of biosorp-tion process. The chapter includes various removal mechanisms suggested for different biosorbents. It also reviews various instru-mental techniques used to elucidate biosorption mechanisms.

Chapter 5 reports various techniques used to prepare bio-sorbents for enhanced performance. Chemical pre-treatment, im-mobilization and genetic modification are discussed.

Chapter 6 lists batch experimental procedure of biosorp-tion process. The influence of experimental parameters such as pH, temperature, biosorbent dosage, biosorbent size, initial solute concentration, ionic strength, agitation rate and contact time on biosorption performance was highlighted. This chapter also lists over 25 isotherm models and several kinetic models for descrip-tion of biosorption experimental data. The errors associated with linearization of non-linear models are also highlighted with ex-amples.

Chapter 7 explains continuous mode of biosorption process. The packed column biosorption process is discussed and the de-termination of parameters is detailed. Column models as well as important results are discussed as well.

Chapter 8 discusses scale-up of the biosorption process to in-dustrial applications. Important aspects discussed in the chapter include, (i) behaviour of biosorbent in real solutions; (ii) applica-bility of biosorption to industrial wastewater treatment processes; (iii) process costs and overall scheme of biosorption; and (iv) devel-opment of practical biosorbent to suit real applications.

Chapter 9 suggests possible application of biosorption in oth-er environmental technologies. It shows how to incorporate bio-sorbents into best management practices such as green roofs and biofilter with illustrations.

Last but not at least, Chapter 10 discusses scope and future directions of biosorption technology.

K. Vijayaraghavan