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Photocatalysis
Applications
RSC Energy and Environment Series

Editor-in-Chief:
Professor Laurence M. Peter, University of Bath, UK

Series Editors:
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Dr Roberto Rinaldi, Max Planck Institute for Coal Research, Germany
Professor Tim S. Zhao, The Hong Kong University of Science and Technology,
Hong Kong, China

Titles in the Series:

1: Thermochemical Conversion of Biomass to Liquid Fuels and Chemicals
2: Innovations in Fuel Cell Technologies
3: Energy Crops
4: Chemical and Biochemical Catalysis for Next Generation Biofuels
5: Molecular Solar Fuels
6: Catalysts for Alcohol-Fuelled Direct Oxidation Fuel Cells
7: Solid Oxide Fuel Cells: From Materials to System Modeling
8: Solar Energy Conversion: Dynamics of Interfacial Electron and
Excitation Transfer
9: Photoelectrochemical Water Splitting: Materials, Processes and
Architectures
10: Biological Conversion of Biomass for Fuels and Chemicals: Explorations
from Natural Utilization Systems
11: Advanced Concepts in Photovoltaics
12: Materials Challenges: Inorganic Photovoltaic Solar Energy
13: Catalytic Hydrogenation for Biomass Valorization
14: Photocatalysis: Fundamentals and Perspectives
15: Photocatalysis: Applications

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Photocatalysis
Applications

Edited by

Dionysios D Dionysiou
University of Cincinnati, Cincinnati, Ohio, USA
Email: dionysios.d.dionysiou@uc.edu

Gianluca Li Puma
Loughborough University, Loughborough, UK
Email: g.lipuma@lboro.ac.uk

Jinhua Ye
National Institute for Materials Science (NIMS), Tsukuba, Japan
Email: Jinhua.YE@nims.go.jp

Jenny Schneider
Leibniz University of Hannover, Hannover, Germany
Email: schneid@iftc.uni-hannover.de

Detlef Bahnemann
Leibniz University of Hannover, Hannover, Germany
Email: bahnemann@iftc.uni-hannover.de
RSC Energy and Environment Series No. 15

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Preface

The field of photocatalysis has experienced numerous applications for the

treatment of water, air, soil and other applications in the field of environ-
mental remediation, self-cleaning surfaces, green chemistry and green
engineering, production of energy and alternative fuels, food packaging
and biomedical and medical applications. The first chapter reviews certain
aspects on the photocatalytic degradation of organic contaminants in water
such as insecticides, chlorinated organic compounds, antibiotics, cyanotox-
ins and taste and odor compounds. Particular emphasis is placed on the role
of water quality parameters on degradation kinetics as well as on degrada-
tion pathways. Chapter 2 discusses the photocatalytic removal of metallic
and other inorganic pollutants such as chromium, mercury, lead, uranium,
arsenic, and nitrate. The chapter discusses mechanistic aspects of energetics
and nano-interfacial phenomena in such process as well as real world appli-
cations. Chapter 3 focuses on solar photocatalytic disinfection of water. The
chapter covers mechanistic aspects of solar disinfection, the role of reactive
oxygen species in the disinfection mechanisms, visible light active materials
and reactors for solar disinfection, and emerging applications of the pho-
tocatalytic inactivation of antibiotic resistant bacteria. Chapter 4 deals with
fundamentals, reactor design and applications of solar photocatalysis. The
chapter includes integration of solar photocatalytic processes with biolog-
ical treatments or membrane processes. Chapter 5 presents development,
characterization and evaluation of combined photocatalysis-separation pro-
cesses for water treatment using hybrid photocatalytic membrane processes.
Chapter 6 presents concepts for the effective integration and coupling of pho-
tocatalytic processes with other treatment processes for the purification of
various types of wastewater. Chapter 7 provides an overview of the photocat-
alytic purification and disinfection of air. The chapter discusses mechanisms

RSC Energy and Environment Series No. 15

Photocatalysis: Applications
Edited by Dionysios D Dionysiou, Gianluca Li Puma, Jinhua Ye, Jenny Schneider,
and Detlef Bahnemann
© The Royal Society of Chemistry 2016
Published by the Royal Society of Chemistry, www.rsc.org

v
vi Preface
of removal of organic contaminants and microbiological airborne objects in
indoor air, the role of various parameters on the mechanisms and kinetics
of removal, commercial and prototype photocatalytic reactors for air purifi-
cation, and present challenges in the field. Chapter 8 reviews development,
mechanisms, applications, progress and challenges in the field of self-clean-
ing photocatalytic materials. Chapter 9 discusses the development, underly-
ing photocatalysis and photoelectrocatalysis mechanisms, and performance
evaluation of PhotoFuelCells for energy generation. Chapter 10 is focused on
photocatalytic hydrogen generation. The chapter presents the mechanism
and reviews applications in the field as well as insights on approaches for
process optimization for higher efficiency. Chapter 11 presents examples of
applications of various photocatalysts in reactions relevant to synthesis of
chemicals. The chapter discusses the role of catalyst type, reaction yields and
selectivities, and concepts of green chemistry and green engineering. The
final chapter (Chapter 12) presents an overview of the potential applications
of TiO2 photocatalysis in food packaging, osseointegration and disinfection
of medical implants, and controlled delivery of chemical compounds.
Contents

Chapter 1 Photocatalytic Degradation of Organic Contaminants in

Water: Process Optimization and Degradation Pathways  1
Maria G. Antoniou, Cen Zhao, Kevin E. O’Shea, Geshan
Zhang, Dionysios D. Dionysiou, Chun Zhao, Changseok Han,
Mallikarjuna N. Nadagouda, Hyeok Choi, Theodora Fotiou,
Theodoros M. Triantis, and Anastasia Hiskia

1.1 I ntroduction  2
1.2 Degradation Efficiency-Kinetics of Emerging
Contaminants  7
1.2.1 Photocatalytic Degradation of Cyanotoxins  7
1.2.2 Photocatalytic Degradation and Detoxification
of Oxytetracycline  7
1.3 Effects of Water Quality Parameters on the
Photocatalytic Degradation of Emerging
Contaminants  9
1.3.1 Effects of General Water Quality Parameters  9
1.3.2 Effects of Natural Organic Matter (NOM) and
Selectivity  11
1.4 Transformation Mechanistic Pathways and Reaction
Intermediates  13
1.4.1 Transformation Products of Compounds
Resulting from the Reaction of Carbon Bonds  14
1.4.2 Transformation Products of Compounds
Resulting from the Reaction of Heteroatoms  24
1.5 Conclusions  29
Acknowledgements  29
References  30

RSC Energy and Environment Series No. 15

Photocatalysis: Applications
Edited by Dionysios D Dionysiou, Gianluca Li Puma, Jinhua Ye, Jenny Schneider,
and Detlef Bahnemann
© The Royal Society of Chemistry 2016
Published by the Royal Society of Chemistry, www.rsc.org

vii
viii Contents
Chapter 2 Photocatalytic Removal of Metallic and Other Inorganic
Pollutants  35
Marta I. Litter, Natalia Quici, J. Martín Meichtry,
and Alejandro M. Senn

2.1 Introduction  35
2.2 Thermodynamical Considerations and
Mechanistic Pathways  38
2.3 Chromium  41
2.4 Mercury  46
2.5 Lead  48
2.6 Uranium  50
2.7 Arsenic  52
2.8 Nitrate  56
2.9 Conclusions  59
References  61

Chapter 3 Solar Photocatalytic Disinfection of Water  72

Pilar Fernández-Ibáñez, J. Anthony Byrne, M. Inmaculada
Polo-López, Patrick S. M. Dunlop, Popi Karaolia,
and Despo Fatta-Kassinos

3.1 Solar Disinfection of Water  72

3.1.1 Solar Spectrum and SODIS Method  72
3.1.2 Oxidative Stress Caused by UV Radiation  73
3.2 Solar Photocatalytic Disinfection of Water  75
3.2.1 Mechanisms of TiO2 Photocatalytic Disinfection  75
3.2.2 Microbiological Aspects of Photocatalytic
Disinfection  77
3.2.3 Inactivation of Antibiotic-Resistant Bacteria  80
3.3 Novel Photocatalytic Materials for Visible Light
Activity  82
3.3.1 Doped Materials  83
3.3.2 Other New Materials  83
3.4 Solar Photocatalytic Reactors for Water Disinfection  85
3.5 Conclusions  87
References  88

Chapter 4 Solar Photocatalysis: Fundamentals, Reactors and

Applications  92
Javier Marugán, María José López-Muñoz,
Pilar Fernández-Ibáñez, and Sixto Malato

4.1 Solar Light  92

4.1.1 Extraterrestrial Irradiance and Spectrum  93
4.1.2 Solar Vector  95
4.1.3 Irradiance at the Earth Surface  96
Contents ix
4.2 Solar Photocatalytic Reactors  102
4.2.1 Types of Reactors  102
4.2.2 Design of Solar Photocatalytic Reactors  103
4.2.3 Solar Reactors for Water Disinfection  104
4.3 Photocatalytic Materials for Solar Applications  108
4.3.1 Titanium Dioxide  108
4.3.2 TiO2 Modification for Solar Applications  109
4.3.3 Mode of Utilisation  113
4.4 Applications of Solar Photocatalysis  116
4.4.1 Non-Concentrating Solar Reactors Applications  117
4.4.2 CPC Solar Reactors Applications  117
4.5 Integration with Other Unit Operations  120
Acknowledgements  123
References  123

Chapter 5 Combined Photocatalysis–Separation Processes

for Water Treatment Using Hybrid Photocatalytic
Membrane Reactors  130
Teik-Thye Lim and Ronn Goei

5.1 Introduction  130

5.2 TiO2 and Application for Water Treatment  132
5.3 Separation Process with Ceramic Membrane  135
5.4 Fabrication of TiO2-Coated Ceramic Membrane  137
5.5 Performance of Photocatalytic Ceramic Membrane  141
5.6 Future Outlook and Challenges  150
References  151

Chapter 6 Process Integration. Concepts of Integration and

Coupling of Photocatalysis with Other Processes  157
Sixto Malato, Pilar Fernández-Ibáñez, Isabel Oller,
Inmaculada Polo, Manuel I. Maldonado,
Sara Miralles-Cuevas, and Ricardo Sánchez

6.1 Introduction  157

6.2 Treatment of Biorecalcitrant Wastewater by
Integrating Solar Photocatalysis and Other
Processes  159
6.3 Partially Biorecalcitrant Wastewater Treatment
by Integrating Solar Photocatalysis and Other
Processes  165
6.4 Removal of Micropollutants in Water and
Wastewater by Integrating Solar Photocatalysis
and Membrane Nanofiltration  167
6.5 Conclusions and Recommendations  171
Acknowledgements  171
References  172
x Contents
Chapter 7 Photocatalytic Purification and Disinfection of Air  174
Alexander Vorontsov

7.1 Introduction  174

7.2 Photocatalytic Reactions for Air Purification  177
7.3 Photocatalysts and Their Supports for Air
Purification  180
7.4 Kinetics of Photocatalytic Oxidation  184
7.5 Photocatalytic Destruction of Microbiological
Objects  189
7.6 Reactors for Photocatalytic Air Treatment  190
7.7 Combined Methods of Air Purification  194
7.8 Conclusions  197
List of Abbreviations and Designations  197
Acknowledgements  197
References  197

Chapter 8 Self-Cleaning Photocatalytic Activity: Materials and

Applications  204
Niall B. McGuinness, Honey John, Maheswari K. Kavitha,
Swagata Banerjee, Dionysios D. Dionysiou,
and Suresh C. Pillai

8.1 Introduction to Self-Cleaning Materials  204

8.2 Mechanism of Self-Cleaning Activity  205
8.2.1 Light-Induced Hydroxylation of the Surface  209
8.2.2 Photo-Oxidation of Adsorbed Hydrocarbons
on the Surface  210
8.3 Photocatalytic Materials  211
8.3.1 Titanium Dioxide  211
8.3.2 Rapid Testing of Self-Cleaning
Photocatalytic Activity  212
8.3.3 Photocatalytic Antibacterial Activity  213
8.4 Semiconductor Doping and TiO2/SiO2 Composites  214
8.4.1 Self-Cleaning Activity  214
8.4.2 Antireflective Properties  216
8.4.3 Metal Doped Coatings  219
8.5 Semiconductor Hybrids and Future Materials  220
8.5.1 Carbon Nanotube Hybrids of TiO2 or ZnO  220
8.5.2 Graphene Hybrids of Metal Oxides  221
8.5.3 Graphene/TiO2 Nanohybrids  222
8.5.4 ZnO/Graphene Nanohybrids  224
8.5.5 TiO2/β Cyclodextrin Encapsulated Fullerene
(C60) Composites  224
8.5.6 Conducting Polyaniline/Metal Oxide or
Graphene Oxide Hybrids  225
Contents xi
8.6 S
 elf-Cleaning and Superhydrophilic Coating on
Polymer Substrates  226
8.7 Commercial Materials  227
Acknowledgements  228
References  228

Chapter 9 Photocatalysis and Photoelectrocatalysis for Energy

Generation Using PhotoFuelCells  236
Panagiotis Lianos, Stavroula Sfaelou, and
Lucian-Cristian Pop

9.1 Introduction  236

9.2 Basic Features of PhotoFuelCell Operation  239
9.3 PhotoFuelCell Configurations and Related
Applications  243
9.4 Selected Results and Discussion  245
9.4.1 PFC Used for Electricity Production
Employing Ethanol as Organic Fuel  245
9.4.2 PFC Used Exclusively for Hydrogen
Production Employing Ethanol as
Organic Fuel  250
9.5 Experimental Section: Construction of
Electrodes and Devices  250
9.5.1 Materials  250
9.5.2 Preparation of TiO2 Films and Deposition
of CdS by the SILAR Method  251
9.5.3 Construction of the Counter Electrode  252
9.5.4 Device (Reactor) Construction  252
9.5.5 Measurements  253
Acknowledgements  253
References  253

Chapter 10 Photocatalytic Hydrogen Generation  255

Xin Li, Jingxiang Low, and Jiaguo Yu

10.1 Introduction  255

10.2 Fundamentals of Photocatalytic Hydrogen
Generation  257
10.2.1 Thermodynamics of Photocatalytic
Hydrogen Generation  257
10.2.2 Materials and Systems for Photocatalytic
Hydrogen Production  259
10.2.3 Mechanisms and Processes of Photocatalytic
Hydrogen Production  264
10.3 Promoted Charge Separation and Transport  265
10.3.1 Improvement of the Crystallinity  265
xii Contents
10.3.2 Rational Design of Nanostructures  266
10.3.3 Application of Carbon-Based Nanomaterials  268
10.3.4 Manipulation of Internal Electric Fields  274
10.4 Accelerated H2-Evolution Kinetics  277
10.4.1 Increasing the Active Surface Areas  277
10.4.2 Loading of H2-Evolution Co-Catalysts  278
10.4.3 Elevation of Conduction Band Positions  283
10.5 Increased Stability of Photocatalyst  285
10.5.1 Addition of Sacrificial Reagents  285
10.5.2 Introduction of a Protective Layer  287
10.5.3 Utilization of Water Oxidation Co-Catalysts  288
10.6 Conclusions, Perspectives and Remarks  289
Acknowledgements  290
References  290

Chapter 11 New Synthetic Routes in Heterogeneous Photocatalysis  303

Giovanni Palmisano, Angelo Albini, Giuseppe Marcì,
Leonardo Palmisano, and Davide Ravelli

11.1 Introduction  303

11.2 Reactions  304
11.2.1 Oxidations  305
11.2.2 Reductions  313
11.2.3 Alkylations  321
11.3 Influence of Catalyst Properties on Selectivity  328
11.4 Green Organic Solvents in Photocatalysis  333
11.5 Conclusion  337
References  337

Chapter 12 An Overview of the Potential Applications of TiO2

Photocatalysis for Food Packaging, Medical Implants,
and Chemical Compound Delivery  345
Pierre Pichat

12.1 Introduction  345

12.2 Potential Advantages of TiO2 Photocatalysis for
Food Packaging  346
12.2.1 Generalities  346
12.2.2 Effect of TiO2 on the Package Physical
Properties  347
12.2.3 Effect of TiO2 on the Package Antibacterial
Properties  347
12.2.4 Effect of TiO2 on the Concentrations of
C2H4 and O2 in Packages  350
12.2.5 Potential Barriers to the Use of TiO2 in
Packages  353
Contents xiii
12.3 R
 oles of TiO2 and TiO2 Photocatalysis in Medical
Implants  353
12.3.1 Role of Non-UV-Irradiated TiO2  353
12.3.2 Roles of UV-Irradiated TiO2  354
12.4 Potential Use of TiO2 Photocatalysis for Chemical
Compound Delivery  356
12.4.1 Generalities  356
12.4.2 Use of TiO2 Nanotubes Containing the
Chemical to be Delivered  357
12.4.3 Use of TiO2 Photocatalysis to Deliver
Chemicals Contained in Microcapsules  360
12.4.4 Issues About the Use of TiO2 Photocatalysis
for Delivery of Chemicals  362
12.5 Conclusions  363
12.5.1 Food Packaging  363
12.5.2 Medical Implants  363
12.5.3 Chemical Compound Delivery  364
12.5.4 Comparisons About the Viability of
These Three Applications  364
References  365

Subject Index  368

     
Chapter 1

Photocatalytic Degradation
of Organic Contaminants in
Water: Process Optimization
and Degradation Pathways†
Maria G. Antoniou*a, Cen Zhaob, Kevin E. O’Sheab,
Geshan Zhangc,d, Dionysios D. Dionysiouc, Chun Zhaoe,
Changseok Hanf, Mallikarjuna N. Nadagoudag,
Hyeok Choih, Theodora Fotioui, Theodoros M.
Triantisi, and Anastasia Hiskiai
a
Department of Environmental Science and Technology, Cyprus University
of Technology, 3036 Lemesos, Cyprus; bDepartment of Chemistry and
Biochemistry, Florida International University, Miami, FL 33199, USA;
c
Environmental Engineering and Science Program, Department of
Biomedical, Chemical and Environmental Engineering (DBCEE),
University of Cincinnati, Cincinnati, OH 45221-0012, USA; dDepartment
of Chemical Engineering, Zhejiang University of Technology, Hangzhou,
Zhejiang, 310014, PR China; eKey Laboratory of the Three Gorges Reservoir

†
The U.S. Environmental Protection Agency, through its Office of Research and Development,
funded and managed, or partially funded and collaborated in, the research described herein.
It has been subjected to the Agency’s administrative review and has been approved for external
publication. Any opinions expressed in this chapter are those of the author(s) and do not nec-
essarily reflect the views of the Agency, therefore, no official endorsement should be inferred.
Any mention of trade names or commercial products does not constitute endorsement or rec-
ommendation for use.

RSC Energy and Environment Series No. 15

Photocatalysis: Applications
Edited by Dionysios D Dionysiou, Gianluca Li Puma, Jinhua Ye, Jenny Schneider,
and Detlef Bahnemann
© The Royal Society of Chemistry 2016
Published by the Royal Society of Chemistry, www.rsc.org

1
2 Chapter 1
Region’s Eco-Environment, Ministry of Education, Chongqing University,
Chongqing 400045, PR China; f ORISE Post-doctoral Fellow, Clean Processes
Branch, Sustainable Technology Division, The United States Environmental
Protection Agency, Cincinnati, OH 45268, USA; g Water Quality Management
Branch, Water Supply and Water Resources Division, National Risk Man-
agement Research Laboratory, The United States Environmental Protection
Agency, Cincinnati, OH 45268, USA; hDepartment of Civil Engineering, The
University of Texas at Arlington, 416 Yates Street, Arlington, Texas 76019-
0308, USA; iCatalytic-Photocatalytic Processes and Environmental Analysis
Lab., Institute of Nanoscience and Nanotechnology, NCSR “DEMOKRITOS”,
Neapoleos 25, Agia Paraskevi, 15341, Athens, Greece
*E-mail: maria.antoniou@cut.ac.cy

1.1 Introduction
Ever since Fujishima and Honda (1972) successfully applied titanium dioxide
(TiO2) for the photoelectrochemical splitting of water, TiO2 has been widely
utilized as a remediation technology for the removal of pollutants from the
air, drinking water, and wastewater.1 TiO2 is considered an attractive alter-
native to other applied technologies because of its superior photo-activity,
low toxicity, chemical and biological inertness, low cost, and corrosion resis-
tance.2,3 TiO2 exists in three different polymorphic forms: anatase, rutile and
brookite with band gaps of 3.2, 3.0, and ∼3.2 eV, respectively, activated in
the UV range. Anatase and rutile are the most common polymorphs, with
the anatase phase possessing higher photocatalytic activity than rutile and
brookite.4 Higher reactivity is associated with the number and type of reactive
oxygen or free radicals species (ROS) formed that react and transform the tar-
geted pollutants first into smaller molecular weight products and ultimately
mineralize them into simpler and non-toxic products H2O, CO2, and mineral
acids. ROS such as hydroxyl radical (HO•), superoxide anion radical (O2−•),
hydroperoxyl radical (HO2•), and singlet oxygen (1O2) are mainly produced
during UV TiO2 photocatalysis.5–7 Hydroxyl radicals, generated on the surface
of the catalyst following oxidation of water from the positive holes of TiO2, are
non-selective oxidizing species with strong oxidation potential (+2.80 V) that
rapidly react with most organic compounds with rate constants of the order
of 106–1010 M−1 s−1.8–10 While several ROS are formed during UV TiO2 photoca-
talysis, the effectiveness of the degradation process is generally dependent on
the production and subsequent reactions of HO• at or very near the TiO2 sur-
face.11,12 The surface adsorption and reactivity of the target compound with
HO• are key factors in the UV promoted TiO2 photocatalytic degradation of
organic compounds. Several heterogeneous kinetic models have been used
to determine apparent kinetic parameters and effectively model the observed
degradation processes.5 Detailed product studies as well as structure–reactivity
Photocatalytic Degradation of Organic Contaminants in Water 3
•
relationships provide convincing evidence that generated HO adsorbed at
the surface of TiO2 has similar reactivity to HO• in a homogenous solution.13
Radiolysis methods are commonly used to study the HO• induced oxidative
degradation of problematic pollutants and toxins. Radiolytic and UV TiO2
photocatalytic degradation of organic compounds can follow similar deg-
radation pathways.14,15 Under photocatalytic conditions the adsorption of a
target compound at a higher surface concentration than in the bulk solution
can enhance the rate of HO• induced degradation since both the oxidant and
target are localized at the surface. For the purpose of this chapter the differ-
ences in reactivities of free and adsorbed HO• will not be discussed.
Hydroxyl radicals generally react with organic compounds via three path-
ways: electrophilic addition (eqn (1.1)), hydrogen atom abstraction (eqn (1.2))
and electron transfer (eqn (1.3)). The hydroxyl radical additions to carbon–
carbon double bonds and electron-rich aromatic systems leading to hydrox-
ylated adducts are generally faster than H-abstraction and electron transfer
pathways. Electron transfer with hydroxyl radical is limited to very electron
rich systems.8 The electron transfer pathway generates a radical cation which
in aqueous media is hydrolyzed, often generating the same hydroxylated
adducts observed by direct addition of HO•. The H-abstraction pathways
result in oxidation of a sp3 hybridized carbon. The hydroxyl radical induced
oxidation of primary (1°), secondary (2°), and tertiary (3°) aliphatic carbons
is initiated by hydrogen atom abstraction. The hydroxyl radical mediated
oxidation of a 1° alcohol via the H-atom abstraction pathways are given in
eqn (1.4). The presence of a heteroatom attached to the carbon significantly
enhances the rate of hydrogen atom abstraction and leads to a stabilized
carbon-centered radical. Such stabilized carbon-centered radicals can add a
molecular oxygen and subsequently eliminate a hydroperoxyl radical to yield
the corresponding oxidation product.
  
RHC=CR2 + HO• → RHC(OH)–C(•)R2 (1.1)
R3C–H + HO• → R3C(•) + H2O (1.2)
RH + HO• → R• + H2O (1.3)
RCH2OH + HO• → RHC(•)OH + O2 → RHC(OO•)OH → RCH(=O) + HO2• (1.4)
  
UV/TiO2 photocatalytic and radiolytic oxidations of benzene and related
aromatic compounds have been extensively studied.16,17 A primary product of
UV/TiO2 photocatalytic degradation of benzene is phenol, which results from
the reaction of HO• addition to the benzene ring. The TiO2 photocatalysis of
benzene involves HO• addition to form hydroxylated and polyhydroxylated
adducts, which upon further oxidation can be converted into quinone type
structures. Subsequent oxidation can also lead to ring open products, afford-
ing low molecular weight carboxylic acids and ultimately CO2. 13C isotope
labeling was used to establish different pathways involved in the formation
of reaction products, muconaldehyde and phenol17,18 (Figure 1.1). Muconal-
dehyde can be readily oxidized to the corresponding carboxylic acids, with
extensive oxidation leading to CO2 as final product. The reaction pathways
 4
Figure 1.1 
Two pathways for TiO2 photocatalysis of benzene. (Reproduced with permission from ref. 17. Copyright 2011 Elsevier.)

Chapter 1
Photocatalytic Degradation of Organic Contaminants in Water 5
leading to muconaldehyde account for 60–70% and pathways via phenol
account for 30–40% of benzene consumption.17
Halogenated organic compounds are among the most problematic water
pollutants. The presence of chlorine, fluorine, bromine, and iodine atoms
can dramatically affect the toxicity and treatability of organic compounds.
Halo-organics have been extensively used as herbicides, pesticides, and in
several personal care products.10,19,20 Because of the negative health envi-
ronmental consequences associated with many halogenated organic com-
pounds extensive studies on TiO2 photocatalytic degradation of halogenated
compounds have been reported.19,20 As an example, the degradation mecha-
nisms of 1,2-dichlorobenzene are initiated with HO• addition to the 3-posi-
tion of 1,2-dichlorobenzene to form 2,3-dichlorophenol (1A) or substitution
of chloro by HO• to generate 2-chlorophenol (1B) (Figure 1.2).19 Intermedi-
ates produced along pathway A are 2,3-dichlorophenol (1A), 2,3-dihydroxy-
chlorobenzene (2A) and 1,2,3-trihydrobenzene (3A) and further oxidation to
CO2. Analogous substitution in pathway B can form 1,2-dihydroxybenzene
(4B) and o-benzoquinone (5B).
Phosphorus, sulfur and nitrogen containing organic substrates are also a
target of TiO2 photocatalytic degradation due to their wide usage for insect
controls in agricultural crops, pharmaceutical, and personal care prod-
ucts.2,21 These heteroatom containing compounds have widespread presence
in groundwater and sediment. While there are numerous successful cases
of remediation of such compounds, we choose to highlight examples of UV/
TiO2 photocatalytic degradation of select phosphorus, sulfur, and nitro-
gen containing compounds. The TiO2 photocatalysis of organophosphorus
insecticides (dimethyl 2,2-dichlorovinyl phosphate and dimethyl 2,2,2-tri-
chloro-1-hydroxyethyl phosphate) has been investigated and the final
degradation products are mineralized to Cl−, PO43−, H+, and CO2.22 The pho-
tocatalytic degradation of sulfur and nitrogen containing molinate under
simulated solar irradiation has been studied using a suspension of TiO2 in
aqueous media.21 Different reaction pathways are involved in the degradation
of molinate by the positive holes and HO•. Ring fragmentation at the amine
group is initiated via hole-mediated oxidation to form an immonium radical
cation which undergoes hydrolysis to yield amine and carboxyl derivatives.23
An H-abstraction pathway leads to the alkyl radical, which undergoes addi-
tion of molecular oxygen with the subsequent elimination of peroxyl radical
to yield keto-molinate. The holes can also mediate oxidation through the sul-
fur atom by an electron transfer process leading to sulfoxide derivatives and
de-alkylated products.21 Extensive treatment can lead to complete mineral-
ization with the formation of NH3, CO2, SO42−, HX, and H2O.
In the following sections, the degradation kinetics of TiO2 photocatalysis
with various pollutants will be extensively discussed along with the effect
of water quality parameters such as pH, natural organic matter (NOM),
and alkalinity. Finally, a thorough discussion of the transformation prod-
ucts formed that lead to the degradation pathways of select compounds is
given.
 6
Chapter 1
Figure 1.2 
Proposed pathways for TiO2 photocatalysis of 1,2-dichlorobenzene. (Reproduced with permission from ref. 19. Copyright
2002 Elsevier.)
Photocatalytic Degradation of Organic Contaminants in Water 7

1.2  egradation Efficiency-Kinetics of Emerging

D
Contaminants
1.2.1 Photocatalytic Degradation of Cyanotoxins
Photocatalysis has become one of the most effective approaches to degrade
highly toxic naturally produced compounds, the cyanotoxins, that cannot be
easily removed through conventional treatment processes. A lot of effort has
been made to investigate the TiO2 photocatalytic degradation of various cya-
notoxins, such as microcystins (MCs) and cylindrospermopsin (CYN), under
UV or solar irradiation. Shephard et al. reported the high degradation effi-
ciency of microcystin-LR (MC-LR) and MC-RR using immobilized TiO2 on a
fiberglass sheet under UVC irradiation with the observed first rate constants
of 0.255 ± 0.017 and 0.199 ± 0.016 min−1, respectively.24 The photocatalytic
degradation of [d-Leu]-MC-LR using Degussa P25 TiO2 film under simulated
solar light was investigated by Vilela et al.25 They reported a treatment time
of 150 min could decrease the toxin concentration from 10 to 1 µg L−1 and
remove 90% initial total organic carbon (TOC) under the experimental con-
dition. Su et al. investigated the high degradation efficiency of MC-LR with
a much higher concentration (5 mg L−1) using TiO2 nanotubes as the pho-
tocatalyst under the irradiation of UV and natural solar light.26 This study
confirmed a better performance of TiO2 nanotubes than TiO2 nanofilm.
Senogles et al. examined the effectiveness of two commercial TiO2 nanoparti-
cles under UV light for the removal of CYN and found Degussa P-25 was more
efficient than Hombikat UV-100.27 In addition, a polymorphic TiO2 nanopar-
ticle investigated by Zhang et al.,28 containing anatase, brookite and rutile
phases, showed good performance for CYN photocatalytic removal.
To extend the light response of TiO2 into the visible region, many studies
focused on the modification of TiO2 by doping with metals (Fe, Co, Ag, or Ni)29
or non-metals (N, F, S, or C).30–33 This causes narrowing of the bandgap of
TiO2 or introduces mid-gap energy states. The study of Choi et al.34 reported
the efficient removal of MC-LR using a self-synthesized nitrogen-doped TiO2
(N–TiO2) under visible light. In addition, the N–TiO2 was found to be 3–4
times more efficient than control TiO2 for the degradation of MC-LR under
UVA irradiation. Another study compared the removal efficiency of MC-LR,
-LA, -YR, -RR, and CYN using N and F doped TiO2 films under visible or UV-vis
irradiation.35 In a mixture of MCs, the reaction rate of an individual toxin
under UV-vis irradiation was shown in this study as follow: MC-LA ≥ MC-LR ≥
MC-YR > MC-RR, which was attributed to the extent of adsorption of an indi-
vidual toxin.

1.2.2  hotocatalytic Degradation and Detoxification of

P
Oxytetracycline
Oxytetracycline (OTC) belongs to tetracyclines, one of the most common
antibiotics group for disease treatment and prevention, and growth promo-
tion in livestock worldwide. Thus, it is one of the most frequently detected
8 Chapter 1
antibiotic chemicals in water bodies and sediments around the world, and
it was also found to be potentially toxic for the ecosystem and humans.36–39
The occurrence of OTC in the environment is due to the discharge of phar-
maceutical, agriculture, and livestock waste. In the past few years, several
studies have demonstrated the presence of OTC in surface water at concen-
trations ranging from a few µg L−1 to mg L−1.40,41 The detoxification of water
by removal of OTC has become a pressing environmental problem because
of the high toxicity of OTC and the inability of conventional treatment pro-
cesses to remove it due to its stable naphthol ring structure and the high tox-
icity to the microorganisms used in biological treatment. Herein, the most
important studies related to the application of TiO2 based photocatalysts for
the treatment of OTC will be presented.
OTC is degradable by both hydrolysis and photolysis. Xuan et al.42 reported
the effects of pH and temperature on the decomposition of OTC. Solution
pH and temperature were found to have important effects on OTC hydrolysis
and photolysis. The hydrolysis was much faster in acidic and alkaline solu-
tions than in neutral. With the enhancement of temperature from 4 ± 0.8 to
60 ± 1 °C, the half-life of OTC reduced from 1.2 × 102 d to 0.15 d. In addition,
the photolytic degradation of OTC was found to be fast with a degradation
rate constant of 3.61 ± 0.06 per day at pH 5.85. The degradation rate is highly
pH dependent and drastically increased in alkaline solutions. OTC has four
species at different pH ranges according to the three ionization equilibrium
constants with pKa values of 3.57, 7.49, and 9.88. The four protonation states
can be represented by H3OTC+, H2OTC, HOTC−, and OTC2−. The adsorption
spectra of OTC at different pH values exhibited a redshift to visible light, par-
alleled to the change of the protonation states of OTC. Zhao et al.43 revealed
a self-photosensitization pathway with evidence of singlet oxygen generation
for HOTC− and OTC2− during photolysis under solar light irradiation. Mean-
while, the three-dimensional fluorescence spectra of OTC at different pH
values also demonstrate that only HOTC− and OTC2− exhibit significant emis-
sion spectra, but not H3OTC+ and H2OTC. Therefore, the change of the inter-
nal electrostatic force of OTC molecule as a function of solution pH values
and species was proposed as a significant factor influencing the energy states
and observed reaction pathways of OTC species under light irradiation. Nev-
ertheless, only 13.5% reduction of TOC occurred despite a rapid photolytic
degradation of 90% of OTC at 20 mg L−1 after 240 min of irradiation by a 500
W medium mercury lamp (light intensity 5.25 × 10−4 W cm−2 at 365 nm).44
Moreover, the photolytic degradation byproducts (maintained the naphthol
ring) have been proved to be even more toxic than the parent when tested
with luminescent bacterium with the inhibition rate increasing from 21% to
47% on P. phosphoreum.44
The photocatalytic removal of OTC with TiO2 was also investigated under
UV, visible, and solar light irradiation. Pereira et al.45 reported the effects
of TiO2 load, solution pH, and inorganic ions on the degradation, miner-
alization, and detoxification of OTC using simulated solar light and nat-
ural solar radiation. The solution pH was critical in decomposing OTC.
Photocatalytic Degradation of Organic Contaminants in Water 9
The highest photocatalytic activity of TiO2 was observed at pH 4.4 and
0.5 g L−1 TiO2 for the removal of both OTC (100% after 40 min of irradiation;
7.5 kJ L−1 of UV dose) and TOC (>90% after 180 min of irradiation; 38.3 kJ L−1
of UV dose), while 100% OTC and ∼80% TOC were removed by 1.8 and
11.3 kJ L−1, respectively, by natural solar energy. In addition, the BOD5
(biological oxygen demand)/COD (chemical oxygen demand) ratio rose from
0 to nearly 0.5, showing a remarkable improvement in biodegradability, while
the inhibition percentage of bioluminescence of Vibrio fischeri decreased
significantly from 35% to 7%. The remaining degradation by-products were
mainly low-molecular-weight carboxylate anions without any antibacterial
activity. The presence of phosphates hindered the removal of OTC, whereas
the presence of chlorides, sulfates, nitrates, ammonium, and bicarbonates
did not alter the degradation kinetics.46 Han et al.47 synthesized Ag-deco-
rated, monodisperse TiO2 aggregates for the degradation of OTC, and found
enhanced photocatalytic activity with a low leaching of Ag in the solution.
Zhao et al.48 also reported the photocatalytic degradation, mineralization,
and detoxification of OTC by 5A and 13X zeolite particles loaded with nano-
TiO2 under UV irradiation. The best loading rate of composite photocatalysts
was 15 wt% TiO2/5A and 10 wt% TiO2/13X for OTC degradation. The compos-
ite photocatalysts showed a better anti-interference capability of radical scav-
engers, and humic acid, at a low concentration than unsupported TiO2 during
the removal of OTC in aqueous solutions.49 Meanwhile, the 10 wt% TiO2/13X
kept the inhibition percentage of bioluminescence of Vibrio qinghaiensis sp.-
Q67 below 35% during the process due to its excellent adsorption capability
of OTC and its degradation byproducts.48 Moreover, the degradation of OTC
was investigated with nitrogen and fluorine doped TiO2 film at different solu-
tion pH under visible and solar light in the presence of a series of scavengers.
Five pathways, including direct photolytic degradation, UV/vis light-induced
photocatalytic oxidation and reduction, and visible light-induced self-
photosensitized oxidation and reduction, were proposed and verified as the
mechanism for OTC photochemical degradation with TiO2.43

1.3  ffects of Water Quality Parameters on the

E
Photocatalytic Degradation of Emerging
Contaminants
1.3.1 Effects of General Water Quality Parameters
The application of TiO2 photocatalysis for the efficient removal of contami-
nants of emerging concern (CEC) is dependent on many different parameters
associated with both water quality and the physical chemical parameters of
the contaminants. The main characteristics of the influent (i.e., pH, alkalin-
ity, dissolved oxygen (DO), and the presence of NOM), the physical chemical
characteristics of the contaminant and the treatment goal will determine the
final design of photocatalytic water treatment systems.50–53 In this section
10 Chapter 1
we review the main publications that investigated the effects of water quality
on the efficiency of TiO2 photocatalysis to remove an array of contaminants.
Pelaez et al.50 reported the effect of water quality parameters on the deg-
radation of the cyanotoxin MC-LR when treated with visible light-active
nitrogen and fluorine co-doped TiO2. Four water parameters (solution pH,
alkalinity, NOM, and DO) were chosen to be studied. The solution pH sig-
nificantly affected the decomposition of MC-LR since it is directly associated
with the surface charge of TiO2 and the contaminant (in this case MC-LR). The
optimal pH range to achieve the highest efficiency for MC-LR decomposition
was 3–4 since TiO2 is positively charged30 and MC-LR is negatively charged at
those pH values,54 which allows the toxin to better interact with the surface
of the catalyst and better utilize the surface formed radicals. The effect of
pH was also observed with other CEC such as carbamazepine (CBZ) when
treated with different types of photocatalysts51,52 such as nitrogen doped
TiO2, conventional TiO2 or zinc oxide (ZnO). For the degradation of CBZ,
the highest degradation was achieved at basic conditions around pH values
of 8–9 using nitrogen doped TiO2.52 At basic conditions, available hydroxyl
ions on the surface of the catalyst increased to form hydroxyl radicals (HO•)
due to changes in the catalyst’s surface ionization states.55,56 Consequently,
increased formation of HO• at these conditions enhanced the photocatalysis
for the decomposition of CBZ. However, when conventional TiO2 and ZnO
were employed to decompose CBZ, the highest degradation was observed at
pH 6.4 when compared to pH 3 and pH 11.51 Therefore, the effect of pH on
the degradation of CEC was found to be dependent on both the targeted CEC
and type of photocatalysts used.
In addition to the effect of pH on the photocatalytic degradation of CEC,
the effect of alkalinity was studied. For the degradation of MC-LR by visi-
ble light-induced photocatalysis, three alkalinity values at 50, 100, and
150 mg L−1 of sodium carbonate were tested at pH 7.1 using a phosphate buf-
fer.50 Increasing alkalinity significantly decreased the degradation of MC-LR
because carbonates and bicarbonates scavenged ROS. Since ROS attack and
decompose CEC in photocatalytic degradation processes, MC-LR degrada-
tion decreased as alkalinity increased. Avisar et al.52 also reported the effect
of alkalinity on the degradation of CBZ under simulated solar light-induced
photocatalysis. In their study, five alkalinity values at 25, 50, 100, 200, and
300 mg L−1 of calcium carbonate (CaCO3) were tested at pH 9.0–9.5. The deg-
radation efficiency of CBZ was also found to be inversely proportional to the
concentration of alkalinity due to the scavenging effect of carbonates and
bicarbonates. Above 200 mg L−1 of CaCO3, the effect of alkalinity on the deg-
radation of CBZ decreased compared to lower alkalinity. It was reported that
the reaction of carbonate and bicarbonate anions with HO• led to the forma-
tion of carbonate radicals, which have a lower redox potential (1.59 V)57 com-
pared to hydroxyl radicals (2.8 V).58 The reduced reactivity of these radicals
resulted in a decrease in the efficiency of the photocatalytic process.
Additionally, the effect of DO on the removal of CEC was investigated
because oxygen has the ability to trap electrons and form additional ROS
Photocatalytic Degradation of Organic Contaminants in Water 11
•−
such as the superoxide anion (O2 ), therefore enhancing photocatalytic pro-
cesses and CEC removal.50,59 The enhancement of photocatalytic degrada-
tion of MC-LR in the presence of DO was also reported.50 Nitrogen or oxygen
was supplied into each solution for 30 min in order to study the effect of
DO on the degradation of MC-LR. The MC-LR degradation rate in the reac-
tor purged with oxygen was higher than that of the nitrogen purged reactor.
The degradation rate was also proportional to the concentration of DO. Since
electron–hole pairs generated during photocatalysis recombined fast in low
concentrations of oxygen, the formation of ROS reduced, and the photocata-
lytic degradation of CEC decreased.60
Finally, the effect of NOM on CEC degradation was investigated since
natural water contains various forms of NOM including humic and fulvic
acids, which can either inhibit or enhance photocatalytic degradation of
CEC.50,53,61,62 For the degradation of MC-LR by visible light-induced photo-
catalysis, the degradation rates were inversely proportional to the concen-
tration of NOM at pH values equal to 3.0, 5.7, and 7.1. Other studies also
reported the inhibition of NOM for the degradation of CEC due to their
scavenging effects of ROS.61,62 Although enhanced photolysis of CEC under
simulated solar irradiation has been reported due to photosensitization of
NOM,63,64 the degradation of CEC was inhibited in the presence of photocat-
alysts such as TiO2 and ZnO. Additional information on the effect of NOM is
discussed in Section 1.3.2.

1.3.2 Effects of Natural Organic Matter (NOM) and Selectivity

The presence of co-existing organic chemicals is problematic in decompos-
ing target chemicals of concern in water. Since hydroxyl radicals produced
from TiO2 non-selectively attack organic chemicals, the decomposition
rates of many organic chemicals seem very similar.55 The non-selective
nature looks attractive because TiO2 photocatalysts do not need special
modification when a target chemical to decompose changes. The photocat-
alytic process does not differentiate one chemical from another in decom-
position. However, this also represents a huge problem when only target
chemicals of concern should be decomposed in a mixture with non-target
chemicals.
In particular, typical source water is contaminated with highly toxic organic
substances at low concentrations (e.g., anthropogenic chemicals such as
pharmaceuticals) and less toxic naturally occurring organic substances at
high concentrations (e.g., NOM). A photocatalytic process is required to focus
on the decomposition of the toxic target chemicals rather than splitting its
reactivity to both toxic targets and non-toxic NOM. However, target chemicals
have to compete with abundant NOM. Competing chemicals take catalytic
sites and consume HO•. Moreover, they foul the surface of TiO2 materials. As
demonstrated in Figure 1.3(a), the presence of humic acid (as representative
NOM) significantly retarded the decomposition of a target chemical, ibupro-
fen (IBP, a well-known analgesic pharmaceutical found in water resources)
12 Chapter 1

Figure 1.3 
Ibuprofen (IBP) decomposition in water by (a) conventional TiO2 (con-
trol) and (b) porous TiO2 in the absence and presence of humic acid
(NOM). The result clearly shows the impact of the presence of NOM and
the significance of the surface modification of TiO2. (Reproduced with
permission from ref. 65. Copyright 2013 Elsevier.)

on conventional TiO2.65 IBP decomposition was significantly decreased to

around 30% in the presence of NOM from 80% in the absence of NOM.
Consequently, nonselective sorption followed by oxidation of co-existing
chemicals at TiO2 surface should be prevented. Operational parameters such
as reaction pH and temperature can change decomposition rates among
organic chemicals while TiO2 materials with controlled properties (e.g., crys-
tal phase) can improve selectivity.66 An extrinsic material exhibiting specific
affinity for a target chemical can also be introduced onto TiO2. Coating TiO2
with molecules with hydrophobic moieties can enhance sorption and oxi-
dation of hydrophobic chemicals.67 Specially designed organic or inorganic
domains as molecular recognition sites are integrated onto TiO2 surface to
preferentially attract targets which then diffuse to the photocatalytic sites
for chemical oxidation.68 Cavities of target chemicals can be imprinted onto
TiO2 surfaces.69 Such chemical modifications exhibit ultimate selectivity only
to target chemicals, meaning that a chemical marker should be replaced
upon change in a target chemical.
Considering the heterogeneous reaction, size-based selection onto
well-defined porous materials has also been investigated. TiO2 particles are
embedded into clay structure and thus molecules smaller than the distance
between sheet silicate layers can reach the embedded TiO2 particles.70 Sim-
ilarly, they can also be coated with a SiO2 shell with well-developed porous
structure.71 However, the approaches discussed above to improve selectiv-
ity commonly require introduction of a secondary material, which generally
decreases overall reactivity due to covered TiO2 surface, reduced UV penetra-
tion, and limited mass transport. A recent study delivered an important mes-
sage that even a pure TiO2 material, when properly designed, can work for
size exclusion (Figure 1.3b).65 TiO2 with well-controlled pores slightly smaller
than NOM and larger than IBP showed improved reactivity towards IBP in the
Photocatalytic Degradation of Organic Contaminants in Water 13
presence of NOM as compared to nonporous control TiO2. However, studies
on preferential photocatalytic degradation in a real mixed stream have still
been rarely reported.

1.4  ransformation Mechanistic Pathways and

T
Reaction Intermediates
Photocatalysis with TiO2 is considered to be an alternative to conventional
methods for environmental detoxification. Its efficiency is based on the for-
mation of ROS that are able to decompose a great variety of environmental
pollutants of different origin (both manmade and naturally found com-
pounds),72–75 functionality (such as pesticides, pharmaceuticals, chlorophe-
nols, and azo dyes),76–79 and chemical structure (organic compounds with
heteroatoms such as N, P, and S).80 Although photocatalysis in the presence
of TiO2 under UV-A proceeds to mineralization of the organic substrates,
the degradation pathways are quite complicated through the formation and
decay of numerous intermediates.81 The elucidation of the reaction mech-
anism is a difficult but necessary task in TiO2 photocatalysis not only for
understanding the process in detail but also for detoxification purposes due
to toxicity and persistency of many intermediates.
Consequently, it is important to monitor together with the destruction of
the parent compounds the formation and decay of the intermediates formed
in order to control all transformation steps, to identify hazardous intermedi-
ates, and to clarify the reaction mechanism.82–84 On some occasions, toxicity
studies are contacted on the treated mixture and/or the identified intermedi-
ates to prove water detoxification following treatment.81
Structural identification of transformation products (TPs) requires
advanced analytical methods that combine high separation efficiency with
increased structural identification capabilities. Due to their high selectiv-
ity and sensitivity, gas and liquid chromatography-mass spectrometry tech-
niques are frequently used methods of choice for the structural elucidation
of TPs.85
Determination of TPs based on mass spectrometry requires three working
steps. Following the exposure of the contaminant of interest to the relevant
treatment, the sample is analyzed using a chromatographic and mass spec-
trometric method optimized for the parent compound. Then the mass spec-
trometer scans a range of masses that account for potential additions on the
contaminant or its fragments. The second step consists of careful examina-
tion of the TP mass spectrum and comparison with the mass spectrum of the
parent compound (contaminant). The final third step consists of additional
analysis by tandem mass spectrometry which insures proper structural iden-
tification of TPs. Following that, TPs can be organized in degradation routes
and pathways.
This section gives an overview of the different intermediates and their
mechanisms of formation upon TiO2 photocatalysis with UV light. For that
14 Chapter 1
reason selected compounds (cyanotoxins i.e. MC-LR, CYN and water taste
and odor compounds, i.e. geosmin (GSM) and 2-methylisoboeneol (MIB))
will be discussed to cover different mechanisms of degradation based on
the functional groups treated with the various ROS that TiO2 photocatalysis
forms. This target group of compounds are emerging contaminants of bio-
logical origin, the photocatalytic degradation of which was recently studied
in detail.6,86–88

1.4.1  ransformation Products of Compounds Resulting

T
from the Reaction of Carbon Bonds
Light activation of titania results in the formation of an array of ROS includ-
ing hydroxyl radicals HO• (main species), superoxide radical anion (O2•−), and
perhydroxyl radical (HO2•−) and the conduction band electron (e−CB).89,90 More
importantly, the positive holes formed in the valence band following electron
photoexcitation can oxidize any compound (organic and/or inorganic) found
adsorbed on the surface of the catalyst, also contributing to the routes of
oxidation.
Since it is not possible to go over all the previously mentioned studies in
this section, select groups of contaminants that incorporate in their struc-
ture basic functional groups (such as aromatic bonds, simple carbon bonds)
and heteroatoms (N) will be discussed as well as their TPs and mechanisms
of formation with TiO2 photocatalysis. The selected group of contaminants
chosen is characterized by great structural variability and concerns a family
of naturally occurring toxins, the cyanotoxins. Cyanotoxins are formed from
the harmful strains of cyanobacterial algal blooms and greatly affect the eco-
system and human health.81,91 They can also be grouped based on structure:
cyclic peptides (microcystins, nodularins–hepatotoxins), alkaloids (saxi-
toxin–neurotoxins), and lipopolysaccharides (LPSs). Cylindrospermopsin
though structurally grouped as an alkaloid is not a neurotoxin but rather
affects the liver and kidneys. Herein, the intermediates of MC-LR, CYN, and
two taste and odor compounds with TiO2 photocatalysis (HO• attack) will be
discussed.
In general, the main mechanistic steps that organic compounds undergo fol-
lowing HO• attack are hydroxylation via substitution or addition with possible
simultaneous isomerization, oxidation, and oxidative bond cleavage. Unsatu-
rated bonds such as aromatic rings and carbon double bonds can undergo
hydroxyl substitution of a hydrogen to form hydroxylated intermediates such
as m/z 1011.5 (Table 1.1). The necessary mechanistic steps include the addi-
tion of a HO• to one of the double bonds and formation of a carbon-centered
radical, which rapidly reacts with oxygen, to form a peroxy radical. The release
of a perhydroxyl radical results eventually in the substitution of the hydrogen
with a hydroxyl group.92 If another HO• reacts with the carbon centered rad-
ical, then hydroxyl addition occurs which changes the carbon hybridization
from sp2 to sp3, and therefore the overall three-dimensional structure of the
TP compared to the parent compound. As will be seen from the studied cases
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De jager maakte zich zoo gauw mogelijk uit de voeten.

De heele familie Spin sprong op den dooden tijger, om hem schoon te

maken en een gedeelte te drogen. Zoo hadden zij weêr vleesch voor
geruimen tijd.

No. 7. Een feest bij de Waternimf.

De watra-mama 137 was de beste vriendin van heer Spin. Wanneer zij
haar maal gereed had, riep zij haar vriend met luide stem en
onmiddellijk kwam heer Spin aan.
 Wanneer zij haar maal gereed had, riep zij haar vriend met luide
stem …—Zie blz. 281.

Ook wanneer heer Spin gekookt had, riep hij zijn vriendin, maar met zóó
zachte stem, dat niemand het hooren kon.

Dit duurde zoo geruimen tijd, tot op zekeren dag de watra-mama een
groot feest gaf op den rivierbodem. Alle boschbewoners waren
uitgenoodigd en ook reeds aanwezig; heer Spin alleen liet op zich
wachten.

Hij was immers te licht en bleef op de wateroppervlakte drijven, waarom

zijn vriend hem aanried, een groote jas aan te trekken en in elken zak
een zwaren steen te doen. Anansi volgde den raad en voegde zich bij
de overige gasten. [282]

„Goeden dag, heer Spin”, klonk het overal.

Een welvoorziene tafel deed Spin watertanden; lag het maar aan hem,
hij zou dadelijk beginnen.

„Een bittertje, màti Anansi?” 138

„Als het U blieft, dat geeft eetlust nietwaar?”

„Zeker”, antwoordde het konijn.

„Aan tafel, mijne heeren”, zei de watra-mama kort daarop.

„Maar màti Anansi, je maakt me beschaamd, trek toch die oude jas uit.”

„O wee!” dacht heer Spin, „nu is alles mis”.

„Kom, vlug wat, vriend”.

„Zuster, je weet toch, dat ik ziek ben, de dokter heeft me

voorgeschreven, mij warm te kleeden, laat ik maar zóó aan tafel gaan”.
„Je komt niet aan tafel met die oude jas”.

Doch heer Spin wilde niet opstaan, om zijn jas uit te trekken.

„Komaan, wat vlugger, alle heeren zijn reeds aan tafel”.

Eindelijk trok heer Spin zijn jas uit, en onmiddellijk rees hij omhoog.

Zoo werd heer Spin voor zijn gulzigheid gestraft.

No. 8. Anansi en Kat.

Heer Spin was bevriend met de ratten, zegt het verhaal. Dagelijks kwam
hij hen bezoeken, om zijn koeroe-koeroe* te laten vullen met hetgeen zij
gestolen hadden. Dit beviel hem uitermate en hij tapte dan ook geregeld
moppen met zijn nieuwe vrienden.

Eens vertelde hij hen, dat hij een kennis had, Ba’ Pina 139 genoemd, die
mooi zong en goed musiceerde. „O, ge moet hem hooren zingen, het is
wel de moeite waard”. [283]

Indien de heeren er niets tegen hebben, zal ik hem eens meebrengen,

dan zal er gedanst moeten worden”.

De ratten keurden het goed.

„Wanneer komt hij dan?”

„Dat mag ik niet beslissen”.

„Breng hem dan meê, als je morgen komt; we zullen zorgen, dat er een
paar dames zijn; wat zullen we een pret maken, jongens!”

Spin ging weg, om met Ba’ Pina te spreken; en deze wilde terstond
meêgaan.
„Neen vriend, wacht tot morgen, dan gaan we samen; en, denk er aan,
dat je dadelijk begint te zingen, als we daar zijn”.

„Zingen? Wat bedoel je daarmede?”

„Wel, miauwen, en een gunstig oogenblik afwachten om aan te vallen,

we deelen eerlijk den buit natuurlijk!”

„Zonder twijfel, vriend”.

„Ze hebben me wel altijd goed onthaald, maar.… ik heb vleesch

noodig”.

„Je neemt toch een korf mede?”

„Ja zeker, en ik zal er jou inzetten, als we aankomen”.

„Wat is dat? Moet ik in jouw korf”.

„Wel, zeker!”

„En waarom?”

„Dwaas, je begrijpt toch wel, dat ze allen wegloopen als zij je aan zien
komen. Daarbij, je bent me veel te voorbarig. Luister naar mij, je zult er
zelf de goede gevolgen van zien. Vragen ze naar je naam, dan zeg je:
Ba’ Pina, niets anders. Dus opgepast”.

„Moet ik niet wat meenemen? Ik heb een moetitte*. Zou deze in je korf
kunnen?” vroeg Ba’ Pina.

Den volgenden morgen ging heer Spin op het gewone uur weg, vond
Ba’ Pina en liet hem plaats nemen in zijn koeroe-koeroe. [284]

„Goeden morgen, dames en heeren!”

„Goeden morgen, broeder! Je hebt ons goed voor den gek gehouden,
waar is jouw muzikant”.
„Hij wilde eerst niet meê komen, daar zijn voeten ziek zijn”.

„Hij maakt immers geen muziek met zijn voeten. Had hem maar
meêgenomen”, riepen de ratten.

„Hij is ook gekomen”.

„Waar is hij, ik zie hem niet”, vroeg een jonge rat.

Spin haalde Ba’ Pina voorzichtig uit den korf. Hij begon te miauwen en
alle ratten dansten om hem heen. Een oude rat, die zijn staart in een val
verloren had, sprak:

„Ik vertrouw dien muzikant even weinig als Spin; hij is heden hier
gekomen met een agasi* waarschijnlijk om er ons in te doen. Houdt
hem in ’t oog, want hij maakt U allen van kant. Ik heb hem meermalen
gezien; sluit hij zijn oogen, dan kunt ge op den dood rekenen”.

De andere ratten luisterden niet en voegden hem toe:

„Je spreekt zoo, omdat je niet meê kunt doen; het is onze schuld toch
niet, dat jij aan jicht lijdt. Kan je niet dansen, ga dan weg!”

„Eén uur van onbedachtzaamheid kan maken, dat men jaren schreit!
Weest voorzichtig met Ba’ Pina; hij zal jelui gauw genoeg opspelden!”

„Ga weg, oud wijf! alles wat je zegt, zeg je uit nijd; het is niets dan nijd!”

De oude rat ging weg. Ba’ Pina begon weêr te zingen en wachtte
ongeduldig op een teeken van anansi, om een aanval te doen. Toen hij
luider begon te miauwen, kwamen uit alle hoeken en gaten de ratten te
voorschijn, om deel te nemen aan de danspartij.

Ba’ Pina hield het niet langer uit, sprong tusschen de aanwezige ratten
en doodde het grootste deel.

„Goed zoo”, zei Spin, „dat heb je netjes gedaan!” [285]

Heer Spin vulde zijn korf; Ba’ Pina at zich zat en vertrok. Waarheen
wordt echter niet verteld.

Anansi bezweek haast onder den last en thuis gekomen, droogde hij de
ratten, waardoor hij weêr voedsel had voor een heel jaar.

„Heb ik niet gelijk gehad?” vroeg de oude rat.

„Ja”, riepen de overgeblevenen, en voortaan gelooven zij wat hij zegt.

Heer Spin durfde nooit meer bij zijne vrienden terug te keeren.

No. 9. Spin en Krekel.

Heer Spin, gedrukt door de zorgen voor zijn groot gezin, kon niet langer
rondkomen met zijn zuur verdiend geld. Hij nam zich voor, op de een of
andere wijze nog wat voedsel machtig te worden en besloot derhalve te
gaan stelen in het korenveld van zijn Opperhoofd.

Na verloop van weken evenwel bemerkte het Hoofd, dat hij bestolen
werd. Vast besloten, niet te zullen rusten voor hij den dief ontdekt had,
liet hij op raad van een zijner dienaren een pop maken van kleefstoffen,
ter grootte van een mensch en deed hij haar plaatsen op het pad, waar
de voetstappen gevonden waren.

Heer Spin, niets wetende, kwam als gewoonlijk met zijn koeroe-koeroe*
op zijn rug.

„Ik groet U, vriend!” zei hij tot de pop.

„.….”

„U antwoordt niet, ga wat op zij en laat me door”.

Heer Spin kreeg nog geen antwoord en gaf toen de pop een slag in ’t
gezicht, maar zijn hand bleef kleven.

„Laat me los, of ik geef je nog een slag!”

Hij gaf de pop een tweeden klap en nog verder kleefde hij vast.

Kort daarna kwam Krekel voorbij, wien heer Spin [286]vriendelijk om hulp
verzocht. Maar toen heer Spin bevrijd was, zat Krekel vast.

Bij het aanbreken van den dag werd hij van de pop afgenomen en
duchtig afgeranseld, terwijl heer Spin zijn hoofd vast hield. Krekel
schreeuwde:

„A no mi, ma no Anansi” 140 waarop heer Spin hem ook een slag gaf,
zich verontschuldigende, dat Krekel zoo onfatsoenlijk aan het schelden
was geweest.

Toen Krekel goed gestraft was, verwijderde heer Spin zich en voortaan
ging hij nu iederen dag in diens korenveld stelen.

No. 10. Heer Spin als Geestelijke.

Heer Spin zit vol listen en streken.

Gedurende een grooten hongersnood kreeg hij van verschillende

vrienden een hoeveelheid aardvruchten, voldoende om hem en zijn
gezin op de been te houden.

Meer en meer teisterde de plaag het dorp, waar heer Spin woonde. De
dorpelingen wisten allen, dat hij een gestudeerde was, en verzochten
hem een gebed aan den barmhartigen God op te zenden.

Heer Spin nam op zich, eenige formulieren naar boven te zenden, op

voorwaarde, dat het volk hem iets zou geven voor de moeite.
Toen zei hij de gebeden op. Het volk was gerustgesteld en schonk hem
tal van belooningen voor de bewezen diensten.

Toen de voorraad op was, dacht heer Spin na, hoe opnieuw aan
voedsel te komen en besloot hij eindelijk, zich voor geestelijke uit te
geven; ’Ma Akoe keurde het goed met lachende lippen.

„Kaptin, joe tjári héde jeri, joe na wan man!” 141 [287]

Heer Spin trok een lange jas met verder toebehooren aan, en ging toen
naar het dorp van het gevogelte, om er te preeken.

Een blinde eend, met zes kleintjes gezegend, hoorde van den nieuwen
geestelijke spreken en zij liet hem tot zich komen, om hem haar leed te
klagen.

Heer Spin kwam met een zwarten bril op en groette het gezin. Daar
begonnen allen te weêklagen. Zij hadden den heelen dag niet gegeten,
want er was niets.
 Heer Spin kwam met een zwarten bril op, en groette het gezin.—
Zie blz. 287.

„Het is immers hongersnood, ik ben toch wel gek, voor andermans

genoegen mijn longen uit te schreeuwen”.

Moeder eend wist niet, wie de geestelijke was en had hem hoog
opgenomen.

Heer Spin verging van honger; hij liet zich daarom door het oudste kind
den waterput aanwijzen, doch doodde het onderweg, at een gedeelte
op en nam de rest mede naar huis.

Zoo deed hij dag aan dag, tot het geheele gezin op deze wijze
verdwenen was.

Heer Spin ging toen overal preeken, maar toen hij het al te bont maakte,
werd hij afgeranseld en verminkt.

De dieren hebben hem weggejaagd uit hun midden, waarom hij zijn
intrek heeft genomen onder de menschen.

De kippen hebben wraak genomen, want zij eten iederen spin op, die zij
tegen komen.

No. 11. Heer Spin als roeier.

Heer Spin ging in dienst bij een dorpshoofd als roeier op een boot,
waarvan de bemanning uit 4 roeiers en een stuurman bestond.

Het Hoofd zei:

„Zoo gaat het niet, ik moet jelui namen weten”.

Heer Spin zei „Tjari gi dem soema”. 142 [288]

Vleermuis riep: „Kot-kóti mofo”. 143

Kikvorsch zei: „Tódo”. 144

Hond antwoordde: „San mi sa taki”. 145

Elken dag zond het dorpshoofd een schotel met lekkere spijzen voor de
bemanning van zijn boot.

Wanneer de bode aankwam, zei hij tot Spin:

„Tjari gi dem soema” dezelfde woorden, die zijn meester hem had
gezegd.

Heer Spin nam geregeld het eten aan, daar de bode zijn naam noemde;
hij at dan alles zelf op en zag er welvarend uit.

Eens op een dag wilde het dorpshoofd een reisje maken. Hij keek de
uitgehongerde roeiers aan en zei:

„Hoe komt het, dat jelui niet roeien?”

„We zijn te zwak”.

„Zwak! Eten jelui dan niet?”

„Neen”, antwoordden drie der roeiers.

„En ik zend iederen dag voedsel!”

„Dat is zoo, maar anansi ontvangt het”.

„Is dat waar?”

„Ja, patron”. 146

„Eten jelui dan niet samen?”

„Neen, ik eet alleen, want U zendt het aan mij alleen”.

„Volstrekt niet! Ik zeg aan den bode: tjari gi dem soema”.

„Dat doet hij ook”.

„En je beweert, dat het voor jou alleen is”.

„Natuurlijk, voor wie anders?”

„Voor jelui allen”.

„Dat wist ik niet”.

„Wat wist je niet?” [289]

„Dat de andere drie zoo heeten”.

„Wat?.… Wat?.… Ik begrijp je niet?”

„Ik heet immers: tjári gi dem soema, niet waar?”

„Ik heb me het voedsel niet toegeëigend! Uwe Excellentie heeft het aan
mij alleen gezonden. U moet voortaan duidelijker instructies geven en
zeggen, dat hetgeen U zendt bestemd is voor ons vieren of vijven, en
niet tjári gi dem soema, want dat ben ik! Indien U het weêr doet, neem
ik het ook weêr aan! Hebt U me verstaan?”

De drie roeiers en de stuurman gaven heer Spin een geducht pak slaag.
Hij vluchtte en liet zijn kleedingstukken achter. Toen is hij gaan schuilen
in hoeken en gaten en durft zich thans niet meer te vertoonen te midden
der andere dieren.

De kakkerlak en zelfs de vliegen spotten met hem.

„Ik zal me wreken”, dacht heer Spin. Hij hing overal netten op, op
eenigen afstand van den grond, om zijn vijanden te vangen.
Sedert dien tijd maakt de spin ijverig jacht op kakkerlakken en vliegen,
en doodt ze, waar zij ze maar vinden kan.

No. 12. Spin neemt Tijger gevangen.

Brutale Spin ging op zekeren dag vriend Tijger bezoeken.

„Wat voor nieuws?”

„Niets”.

„Zeg mij toch, Spin, zou jij in staat zijn den tijger te berijden?”

„Of ik in staat ben een tijger te berijden? Wel natuurlijk! Ik zal jou
berijden, zoodra je me maar de gelegenheid geeft”.

„Dat lieg je, kwast”.

„En ik zeg je, dat ik je op stal zal brengen en je gevangen zal nemen.—
Neem je de weddenschap aan?”

„Zeker”. [290]

„Wel, morgen ochtend om acht uur rijd ik je, zonder uitstel”.

Den volgenden morgen, omstreeks half acht, stond Heer Spin in

Gouverneurs-uniform gereed en zette zich in het gras naast den weg,
waar Tijger voorbij moest gaan. Toen hij hem aan zag komen, begon hij
in het gras te rollen en te roepen, dat hij buikpijn had.

Tijger sprak hem aan:

„Jij zoudt me immers op dit uur berijden, niet?”

„Dat heb ik gezegd, dat is zoo, maar zonder na te denken. Jij kent mij
toch met mijn bluffen. Hoe zou ik dat kunnen, ik arm, krachteloos dier,
jou als rijdier gebruiken! Wees wijzer, heb medelijden met mij, ik verga
van pijn, mijn aars* is heelemaal uitgekomen”.

De Spin had een rijstzak bij zich met hoofdstel, leidsels, zadel, enz. er
in.

„Bekijk dezen zak, ik kan hem niet eens dragen, hoe zou ik jou kunnen
berijden?”

Spin lag bewusteloos neêr.

„Vriend Tijger, kijk niet naar mij, luister niet naar mijne woorden, maar
heb medelijden met mij, anders ga ik hier sterven; laat me op je rug
gaan zitten”.

Tijger, die medelijden kreeg met hem, stond het hem toe.

Spin had veel moeite, om er op te komen.

„Mijn aars”, schreeuwde hij, „mijn anus doet me zoo’n pijn! Sta me toe,
vriend, iets zachts op je rug te leggen, anders loop ik gevaar, dat mijn
darmen geheel uitkomen”.

„Zooals je wilt”.

Spin zadelde Tijger, dat het de moeite waard was. „Men kan niet zitten
zonder steun, niet waar vriend?”

„Houd dit priemetje in je bek. Vlug wat, wil je soms de baas gaan spelen
voor mijn goedheid?”

„Welneen, vriend”.

„Gauw dan, want ik moet weg”. [291]

Spin besteeg Tijger, die in galop wegholde.

Hij had zijn zin gekregen; hij zweepte Tijger, sloeg hem met de sporen,
bracht hem voor het huis van het dorpshoofd en zei tegen den knecht:

„Neem mijn paard en breng het op stal”.

Men deed, wat hij vroeg, en Tijger werd in den stal opgesloten.

„Heb ik je niet gezegd, dat ik je zou berijden en gevangen nemen? Nu

zit je in de kooi en je hebt er je zelf ingebracht, ezel die je bent” en heer
Spin ging heen.

Boen no habi tangi. 147

No. 13. Heer Spin en Hond.

Zeker dorpshoofd, heel goed met heer Spin bekend, nam zich voor,
hem eens aan de kaak te stellen.

Hij liet twee koeien, een vette en een magere, in een stal plaatsen, die
geheel gesloten was. De magere koe werd met trommelkoord, de
andere met naaigaren vastgebonden; de twee uiteinden werden door
een gaatje, dat in een der planken geboord was, heengestoken.

Heer Spin en vriend Hond werden daarop door het Hoofd uitgenoodigd.

„Ik heb twee koeien op stal”, zei deze, „een vette en een magere: de
eene is vastgebonden met trommelkoord, de andere met naaigaren;
neemt elk een van de uiteinden en ge moogt de koe, die er aan
vastgebonden is, hebben”.

Heer Spin vloog naar den stal en nam het trommelkoord; Hond, die later
kwam, moest zich met het naaigaren tevreden stellen.
Anansi meende, dat een flink beest niet met naaigaren vastgebonden
kan worden en verheugde zich een goeden [292]slag geslagen te
hebben; doch toen de stal geopend werd, moest aan hem de magere
en aan Hond de vette koe gegeven worden.

Heer Spin was daarmeê echter niet tevreden en stelde Hond voor, te
verwisselen.

„Vriend, wees tevreden met je lot, ik voor mij ruil niet.”

„Goed, laat het dan zoo blijven; ik wil ook niet meer ruilen, ik ga mijn
koe slachten”.

Heer Spin gaf aan Hond de lever en een stukje vleesch. Daarna togen
zij samen op weg.

„Mati dagoe 148 geef me de lever terug”, zei anansi en Hond deed het.

„Jij bent toch een onverdraagzame kerel, men kan met jou nooit eens
een mop tappen”.

Hond liet zich dit niet zeggen en nam de lever weêr in zijn bek.

Eenige oogenblikken later begon heer Spin weêr:

„Geef me de lever terug”.

Hond deed andermaal wat hem gevraagd werd.

„Ik zal van mijn leven nooit meer een grap met jou hebben. Wat ben je
dom!” zei Anansi.

Weder nam Hond de lever terug, ging toen wat drinken en slikte de
lever in. Spin bemerkte het.

„Vriend, tot dusverre heb ik geschertst, maar nu is het ernst; geef me de

lever terug, anders krijgen we ruzie”.
Doch Hond kon niet spreken, en knorde:

„Ik heb haar bij vergissing ingeslikt”.

„Bij vergissing ingeslikt! Ik moet die lever terug hebben, al zou je je

eigen koe moeten slachten; ik moet haar terug hebben”.

Hond slachtte daarop zijn koe en gaf Anansi het gevraagde stuk.
Daarop liep hij weg en maakte hij een [293]groot gat, waarin hij zich
verschool, om heer Spin zijn onhebbelijkheid betaald te zetten.

Toen Anansi aankwam, begon hij te knorren en liet hij de tanden zien.
Heer Spin dacht, dat het de aarde was, die lachte; zette zijn koeroe-
koeroe* neêr en sprak:

„Ik verzoek mijn vader, mij door te laten”.

Hond begon dof te blaffen.

„Gij verlangt zeker een stuk vleesch, niet?”

Heer Spin gooide een stuk vleesch naar beneden, doch Hond begon
nog harder te blaffen. Anansi werd doodsbang.

„Wil je nog een stuk?”

Heer Spin wierp weêr een stuk, hetgeen hij herhaalde tot hij niets meer
had. Toen liep hij naar het dorpshoofd, deelde hem het voorgevallene
mede. Het hoofd wist, dat Anansi een leugenaar was, en geloofde het
verhaal niet.

„Indien ik lieg, wil ik mijn hoofd verliezen”, riep Anansi.

Twintig soldaten gingen daarop met hem mede, maar ze zagen slechts
een grooten kuil.