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Environmental Chemistry for a Sustainable World
Eric Lichtfouse • Jan Schwarzbauer
Didier Robert
Editors

Environmental Chemistry
for a Sustainable World
Volume 1: Nanotechnology
and Health Risk
Editors
Eric Lichtfouse Jan Schwarzbauer
INRA, UMR Agroécologie RWTH Aachen
Dijon, France Inst. für Geologie, Geochemie u.
eric.lichtfouse@dijon.inra.fr Lagerstätten d. Erdöls u. d. Kohle
www.researcherid.com/rid/F-4759-2011 Lochnerstr. 4-20, 52056 Aachen
Germany
Didier Robert schwarzbauer@lek.rwth-aachen.de
Lab. of de Chimie Industrielle
rue Victor Demange
Université de Metz
57500 Saint-Avold
France
didier.robert@iut.univ-metz.fr

ISBN 978-94-007-2441-9 e-ISBN 978-94-007-2442-6

DOI 10.1007/978-94-007-2442-6
Springer Dordrecht Heidelberg London New York
Library of Congress Control Number: 2011942487

© Springer Science+Business Media B.V. 2012

No part of this work may be reproduced, stored in a retrieval system, or transmitted in any form or by any
means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written
permission from the Publisher, with the exception of any material supplied specifically for the purpose
of being entered and executed on a computer system, for exclusive use by the purchaser of the work.

Printed on acid-free paper

Springer is part of Springer Science+Business Media (www.springer.com)

Preface

I was at a conference where someone said something about the

Holocene. I suddenly thought this was wrong. The world has
changed too much. So I said: ‘No, we are in the Anthropocene.’
I just made up the word on the spur of the moment. Everyone
was shocked. But it seems to have stuck.
Nobel Prize-winner Paul Crutzen

To find rapidly chapters of interest in this book please see list of topics in Table 1 page ix.

Fukushima, Chernobyl and Climate Change

Nuclear Plants on Earthquake Zones

Everybody has been recently shocked by the major accident of the nuclear power
plant on March 31, 2011 at Fukushima, Japan. Such a failure was both unexpected
and expected. Unexpected because most thought that the 1986 nuclear disaster at
the power plant of Chernobyl, Ukraine, could never happen again, especially in
wealthy, high technology countries such as Japan. Expected because geology tells
us that Japan lies on the cusp of the Pacific-Philippine-Eurasian triple plate junction,
where the complex interactions of three tectonic plates is unpredictable and loaded
with potential activity. As a consequence, Japan experiences regular, high intensity
earthquakes, tsunamis and volcanoes since centuries. Similarly to the Chernobyl
global ‘event’, the release of radioactive pollutants from Fukushima nuclear plant in
water, air, and soil will most probably severely affect human health, food security
and economy worldwide for decades. Therefore, one might just ask why nuclear
plants are built on such high-risk areas.

v
vi Preface

Human Errors Are Repeatable

The global warming event has similar features – though less rapid and catastrophic
– as the Chernobyl and Fukushima events on several rationales. First, the global
warming is a worldwide event due notably to worldwide CO2 emissions (Lichtfouse
2009a), a fact that is nicely coined by the popular saying “pollutants have no bor-
ders”. Second, the effects of global warming are now clearly proven by many scien-
tific trends (Feehan et al. 2009; Jones et al. 2009; Lavalle et al. 2009). Third, despite
all such scientific evidence humans still use cars and planes that emit CO2; they
practice intensive, industrial agriculture that decrease soil carbon, and in turn emits
CO2; they cut forest, which in turn emits CO2, and so on. Recent essays reports on
global issues of and solution for society (Lichtfouse 2009a, b, 2010). From the sci-
entist view, one might say ironically that “human errors are repeatable”.

Social Chemistry

From those global issues several conclusions and advices can be drawn to improve
society and the life of further generations. First, overwhelming scientific evidence
is not sufficient to convince humans, notably decision-makers. Such a failure is due
in particular to the lack of communication between science and society. In other
words, scientists should not only publish in scholarly journals and attend high-level
scientific meetings, but also communicate with the “real world”. Here, a “social
impact factor” to measure the impact of science on society – based for instance on
web, facebook and blog usage data – would be very appreciated.
A second advice is that classical natural sciences such as chemistry, physics,
biology, geology and medicine should integrate social, human and political sciences.
In other words, the real world should be involved in the process of scientific discovery
to bridge the gap between science and people. The integration of social disciplines
is already occurring in agrosciences (Fleming and Vanclay 2010; Karami and
Keshavarz 2010; Lichtfouse 2010; Lichtfouse et al, 2009, 2010). Indeed agriculture
has always been historically closer to citizens, e.g. farmers, than chemistry and
physics. The need for analysis of citizen discourses is nicely shown by the following
survey answer: ‘What’s sustainable? You’ve got to look at our world as we know it.
We’re not in a sustainable position at the moment. That’s why I say what is sustainable
– I don’t know’ (Fleming and Vanclay 2010).
The concept of discourse was introduced in the 1960s by the French philosopher
Michel Foucault. Foucault (1972) maintained that the way language is used has
consequences for a whole range of things that go beyond the level of individuals or
disciplines, to the very structures of society that shape and limit how people are able
to speak, think, and act, and to the social structures that are developed accordingly.
Now, environmental chemistry should use techniques of social sciences such as
discourse analysis to discover novel findings that will be both innovative and
accepted by citizens.
Preface vii

The Success of Environmental Chemistry

Association of Chemistry and the Environment

We founded the Association of Chemistry and the Environment in 2000 with a

group of environmental scientists (www.europeanace.com). A “chemistry flower”
logo was designed to symbolise positive benefits of chemistry for Nature (Fig. 1).
The association was launched by the organisation of the two first European Meeting
on Environmental Chemistry by Eric Lichtfouse, Brigitte Elbisser and co-workers
in 2000 in Nancy, France, and in 2001 in Dijon, France. Meetings were immediately
a success, with more than 300 attendants, due to several factors such as hard work
from the organising team, willingness to create a new science community in a highly
conservative science system, and gathering in a friendly location scientists from
various isolated disciplines such as soil science, toxicology and chemistry. The
first presidents of the association were Eric Lichtfouse (2000–2004) and Jan
Schwarzbauer (2005–2009). Noteworthy, well established associations, in particu-
lar the Division of Environmental Chemistry and the Division of Geochemistry of
the American Chemical Society (ACS), supported us, in particular by organising
joint symposia sponsored by the petroleum research fund. We therefore thank very
much the American Chemical Society.

Fig. 1 The “chemistry

flower” was designed by Eric
Lichtfouse and Guillaume
Decaux to symbolise positive
benefits of chemistry for
Nature. Guillaume Decaux is
a professional drawer living
in Strasbourg, France (http://
www.alcide.fr/)
viii Preface

Fig. 2 The impact factor of

the journal Environmental Impact Factor
Chemistry Letters ( ECL) Environmental Chemistry Letters
increased from 0.814 in 2006
3
to 2.109 in 2009. Article pdf
downloads reached 36,549 in
2009 (100 per day)

0
2005 2006 2007 2008 2009 2010

Environmental Chemistry Letters

We founded the journal Environmental Chemistry Letters in 2003 to fill the science
gap between chemistry and environment (www.springer.com/10311). Despite a
tough selection by the Thomson Reuters agency to enter the Science Citation Index,
we got our first impact factor of 0.814 for 2006, only 3 years later. The impact factor
increased steadily to reach 2.109 in 2009 (Fig. 2) (www.thomsonreuters.com). The
increase of the impact factor can be explained by a higher quality of articles, as a
result of higher rejection that reached 73% in 2009. Given the rapid increase of sub-
mitted articles, more that 70% of articles are now declined at pre-screening stage.
Journal articles are highly viewed as proven by the number of pdf downloads that
reached 36,549 in 2009 (100 per day). This finding is both unexpected and expected.
Unexpected because most articles are not in open access. Expected because Springer
has about 30 millions scientists who access articles. Here, contrarily to the common
thinking, articles published in restricted access by a major publisher are probably
much more visible than open access articles published by a minor publisher.

Environmental Chemistry

We published the book Environmental Chemistry in 2005 (Lichtfouse et al. 2005b).

The book includes 69 chapters sorted in seven sections: Analytical Chemistry, Toxic
Metals, Organic Pollutants, Polycyclic Aromatic Hydrocarbons, Pesticides, Green
Chemistry, and Ecotoxicology. The book is a success with over 35,000 chapter down-
loads from 2007 to 2010. Book chapters are still highly downloaded with 639
 Preface

Table 1 Chapters of environmental chemistry for a sustainable world (Lichtfouse et al. 2012a, b)
1st author Keywords DOI
Tan Nanotubes Energy Water 10.1007/978-94-007-2442-6_1
Landy Cyclodextrin Sequestration Water 10.1007/978-94-007-2442-6_2
Chauhan Nanotubes Energy Sensors 10.1007/978-94-007-2442-6_3
Liu Photocatalysis Remediation Water 10.1007/978-94-007-2442-6_4
Visinescu Polysaccharides Metal oxides Green chemistry 10.1007/978-94-007-2442-6_5
Ricking DDT isomers Remediation Pesticides 10.1007/978-94-007-2442-6_6
Heim Geochronolgy Pollution history Sediments 10.1007/978-94-007-2442-6_7
Anupama Endocrine disruptors Toxicity Pesticides 10.1007/978-94-007-2442-6_8
Stankovic Heavy metal Toxicity Seafood 10.1007/978-94-007-2442-6_9
Sarkar DDT, PCBs Toxicity Seafood 10.1007/978-94-007-2442-6_10
Ribeiro Pharmaceuticals Remediation Water 10.1007/978-94-007-2439-6_1
Sanjurjo Buildings CO2, SO2, NOx Air 10.1007/978-94-007-2439-6_2
Rene Bioreactors Remediation VOCs 10.1007/978-94-007-2439-6_3
Etxebarria Extraction Pollutants Water 10.1007/978-94-007-2439-6_4
Sharma ClO2, R-Cl Oxidation Water 10.1007/978-94-007-2439-6_5
Mondal Dyes Biodegradation Water 10.1007/978-94-007-2439-6_6
Shukla Heavy metals Lichens Air 10.1007/978-94-007-2439-6_7
Brillas Pharmaceuticals Remediation Water 10.1007/978-94-007-2439-6_8
López Biogas Cleaning CO2, H2S, R-Cl 10.1007/978-94-007-2439-6_9
Mudhoo Heavy metals Toxicity Biosorption 10.1007/978-94-007-2439-6_10
Gasparatos Heavy metals Sequestration Nodules, soil 10.1007/978-94-007-2439-6_11
Dabrowska Arsenic Remediation Biosorption 10.1007/978-94-007-2439-6_12
Mahmood Photocatalysis Microbes Disinfection 10.1007/978-94-007-2439-6_13
Keywords and DOI for fast access. DDT 2,2,-bis(4-chlorophenyl)-1,1,1-trichlorethane, PCBs polychorinated biphenyls, VOCs volatile organic compounds
ix
x Preface

downloads in January 2011 (20 per day). The highest recent downloads can be freely
viewed at Springer Realtime (www.realtime.springer.com). Here the most popular
topics are heavy metals, bioremediation and green chemistry.

Environmental Chemistry for a Sustainable World

This new book series presents 23 chapters published into 2 volumes: Nanotechnology
and Health Risk (Lichtfouse et al. 2012a), and Remediation of Air and Water
Pollution (Lichtfouse et al. 2012b). Table 1 allows fast access to chapters by topics.
All chapters have been reviewed and the rejection rate was 15%. The Nanotechnology
section highlights carbon nanotubes for energy and detection; cyclodextrins for pol-
lutant trapping; magnetic nanophotocatalysts for pollutant degradation; and poly-
saccharides for metal oxide green synthesis. The Health Risk section describes new
findings on the old DDT pesticide; geochronology of river pollutants; toxic effects
of endocrine disruptors; and heavy metals in seafood. The Air and Water Pollution
section presents the selective degradation of chiral pharmaceuticals; the alteration
of housing walls by CO2, SO2 and NOx; cleaning industrial waste gas and dyes
wastewater; methods to extract and detect pollutants; and harmful chlorinated
pollutants. The Remediation section highlights the electrochemical degradation of
pharmaceuticals; methods to treat biogas CO2, CH4, H2S and NH4; heavy metal
sequestration on biomass and soil nodules; As phytoremediation; and photocata-
lytic inactivation of water microbial pathogens.

Eric Lichtfouse,
Jan Schwarzbauer,
Didier Robert

References

Feehan J, Harley M, Minnen J (2009) Climate change in Europe. 1. Impact on terrestrial ecosystems
and biodiversity. A review. Agron Sustain Dev 29:409–421. doi:10.1051/agro:2008066
Fleming A, Vanclay F (2010) Farmer responses to climate change and sustainable agriculture.
A review. Agron Sustain Dev 30:11–19. doi:10.1051/agro/2009028
Foucault M (1972) The archaeology of knowledge: and the discourse on language. Tavistock
Publications Ltd, London, 249 p. ISBN 0-415-28753-7
Jones A, Stolbovoy V, Rusco E, Gentile AR, Gardi C, Marechal B, Montanarella L (2009) Climate
change in Europe. 2. Impact on soil. A review. Agron Sustain Dev 29:423–432. doi:10.1051/
agro:2008067
Karami E, Keshavarz M (2010) Sociology of sustainable agriculture. In: Lichtfouse E (ed)
Sociology, organic farming, climate change and soil science. Sustain Agric Rev 3:19–40.
doi:10.1007/978-90-481-3333-8
Lavalle C, Micale F, Durrant Houston T, Camia A, Hiederer R, Lazar C, Conte C, Amatulli G,
Genovese G (2009) Climate change in Europe. 3. Impact on agriculture and forestry. A review.
Agron Sustain Dev 29 (2009):433–446. doi:10.1051/agro/2008068
Preface xi

Lichtfouse E (2009a) Climate change, society issues and sustainable agriculture. In: Lichtfouse E
(ed) Climate change, intercropping, pest control and beneficial microorganisms. Sustain Agric
Rev 2:1–7. doi:10.1007/978-90-481-2716-0_1
Lichtfouse E (2009b) Sustainable agriculture as a central science to solve global society issues. In:
Lichtfouse E (ed) Organic farming, pest control and remediation of soil pollutants. Sustain
Agric Rev 1:1–3. doi:10.1007/978-1-4020-9654-91
Lichtfouse E (2010) Society issues, painkiller solutions, dependence and sustainable agriculture.
In: Lichtfouse E (ed) Sociology, organic farming, climate change and soil science. Sustain
Agric Rev 3:1–17. doi:10.1007/978-90-481-3333-8_1
Lichtfouse E, Schwarzbauer J, Robert D (2005a) Preface. In: Lichtfouse E, Schwarzbauer J, Robert
D (eds) Environmental chemistry, vol 1, p V. Springer, Berlin. doi:10.1007/b137751
Lichtfouse E, Schwarzbauer J, Robert D (2005b) (eds) Environmental chemistry, vol 1, p V.
Springer, Berlin. ISBN 978-3-540-22860-8. doi:10.1007/b137751
Lichtfouse E, Navarrete M, Debaeke P, Souchère V, Alberola C, Ménassieu J (2009) Agronomy for
sustainable agriculture. A review. Agron Sustain Dev 29:1–6. doi:10.1051/agro:2008054
Lichtfouse E, Hamelin M, Navarrete M, Debaeke P, Henri A (2010) Emerging agroscience. Agron
Sustain Dev 29:1–10. doi:10.1051/agro/200955
Lichtfouse E, Schwarzbauer J, Robert D (2012a) Environmental chemistry for a sustainable world.
Volume 1: nanotechnology and health risk. Springer, Dordrecht, 458 p. doi: 10.1007/978-94-
007-2442-6
Lichtfouse E, Schwarzbauer J, Robert D (2012b) Environmental chemistry for a sustainable world.
Volume 2: remediation of air and water pollution. Springer, Dordrecht, 562 p. doi: 10.1007/978-
94-007-2439-6
Other Publications by the Editors

Books

Environmental Chemistry
ISBN: 978-3-540-22860-8

Organic contaminants in riverine and ground water systems. Aspects of the anthro-
pogenic contribution
ISBN: 978-3-540-31169-0

Sustainable Agriculture
ISBN: Vol. 1: 978-90-481-2665-1
ISBN: Vol. 2: 978-94-007-0393-3

Rédiger pour être publié! Conseils pratiques pour les scientifiques

ISBN: 978-2-287-99395-4

Journals

Environmental Chemistry Letters

ISSN: 1610-3653
http://www.springer.com/10311

Agronomy for Sustainable Development

ISSN: 1774-0746
http://www.springer.com/13593

Book series

Sustainable Agriculture Reviews

ISSN: 2210-4410
http://www.springer.com/series/8380
xiii
Contents

Part I Nanotechnology

1 Carbon Nanotubes Applications: Solar and Fuel Cells,

Hydrogen Storage, Lithium Batteries, Supercapacitors,
Nanocomposites, Gas, Pathogens, Dyes, Heavy Metals
and Pesticides........................................................................................... 3
Chin Wei Tan, Kok Hong Tan, Yit Thai Ong, Abdul Rahman Mohamed,
Sharif Hussein Sharif Zein, and Soon Huat Tan
2 Cyclodextrins for Remediation Technologies ....................................... 47
David Landy, Isabelle Mallard, Anne Ponchel, Eric Monflier,
and Sophie Fourmentin
3 Carbon Nanotubes for Environmental Protection ............................... 83
Sippy K. Chauhan, Anuradha Shukla, Simpi Dutta, S. Gangopadhyay,
and Lalit M. Bharadwaj
4 Magnetic Nano-photocatalysts: Preparation, Structure,
and Application ....................................................................................... 99
Shou-Qing Liu
5 Polysaccharides Route: A New Green Strategy
for Metal Oxides Synthesis ..................................................................... 119
Diana Visinescu, Greta Patrinoiu, Alina Tirsoaga, and Oana Carp

Part II Health Risk

6 Environmental Fate of DDT Isomers and Metabolites ........................ 173

Mathias Ricking and Jan Schwarzbauer
7 Geochronology of Anthropogenic Contaminants
in Aquatic Sediment Archives ................................................................ 209
Sabine Heim and Jan Schwarzbauer

xv
xvi Contents

8 Organic Pollutants as Endocrine Disruptors: Organometallics,

PAHs, Organochlorine, Organophosphate and Carbamate
Insecticides, Phthalates, Dioxins, Phytoestrogens,
Alkyl Phenols and Bisphenol A .............................................................. 259
P. R. Anupama Nair and C.H. Sujatha
9 Heavy Metals in Seafood Mussels. Risks
for Human Health ................................................................................... 311
Slavka Stankovic, Mihajlo Jovic, Ana R. Stankovic, and Lynne Katsikas
10 Persistent Organic Pollutants (POPs) in Sediments
and Biota in Coastal Environments of India ........................................ 375
S.K. Sarkar, K.K. Satpathy, M.P. Jonathan, A. Bhattacharya,
A. Alam, M. Chatterjee, B.D. Bhattacharya, and S.N. Biswas

Index.............. ................................................................................................... 407

Contributors

A. Alam Department of Marine Science, University of Calcutta, 35 Ballygunge

Circular Road, Calcutta West Bengal 700 019, India
Lalit M. Bharadwaj Biomolecular Electronics and Nanotechnology, Central
Scientific Instruments Organization (CSIR), Chandigarh, India
A. Bhattacharya Department of Marine Science, University of Calcutta, 35
Ballygunge Circular Road, Calcutta, West Bengal 700 019, India
B.D. Bhattacharya Department of Marine Science, University of Calcutta, 35
Ballygunge Circular Road, Calcutta, West Bengal 700 019, India
S.N. Biswas Department of Marine Science, University of Calcutta, 35 Ballygunge
Circular Road, Calcutta 700 019, India
Oana Carp Coordination and Supramolecular Chemistry Laboratory, Institute of
Physical Chemistry “Ilie Murgulescu”, Romanian Academy, Splaiul Independentei
202, 060021 Bucharest, Romania, carp@acodarom.ro
M. Chatterjee Department of Marine Science, University of Calcutta,
35 Ballygunge Circular Road, Calcutta, West Bengal 700 019, India
Sippy K. Chauhan Traffic Planning and Environment Division, Central Road
Research Institute (CSIR), New Delhi 110020, India, chauhansippy4@yahoo.co.in
Simpi Dutta Traffic Planning and Environment Division, Central Road Research
Institute (CSIR), New Delhi 110020, India
Sophie Fourmentin Unité de Chimie Environnementale et Interactions sur le Vivant
(EA 4492), Université du Littoral-Côte d’Opale, 145, Avenue Maurice Schumann,
MREI 1, 59140, Dunkerque, France, sophie.fourmentin@univ-littoral.fr
S. Gangopadhyay Traffic Planning and Environment Division, Central Road
Research Institute (CSIR), New Delhi 110020, India

xvii
xviii Contributors

Sabine Heim Laboratory for Organic-geochemical Analysis, Institute of Geology

and Geochemistry of Petroleum and Coal, RWTH Aachen University, Lochnerstr.
4-20, 52056, Aachen, Germany, heim@lek.rwth-aachen.de
M.P. Jonathan Centro Interdisciplinario de Investigaciones y Estudios sobre
Medio Ambiente y Desarrollo (CIIEMAD), Instituto Politécnico Nacional (IPN),
Calle 30 de Junio de 1520, Barrio la Laguna Ticomán, Del. Gustavo A. Madero,
C.P.07340 Mexico, D.F, Mexico, mpjonathan7@yahoo.com
Mihajlo Jovic Faculty of Technology and Metallurgy, University of Belgrade,
Karnegijeva 4, 11 000 Belgrade, Serbia, jovicmihajlo@yahoo.co.uk
Lynne Katsikas Faculty of Technology and Metallurgy, University of Belgrade,
Karnegijeva 4, 11 000 Belgrade, Serbia, lynne@tmf.bg.ac.rs
David Landy Unité de Chimie Environnementale et Interactions sur le Vivant
(EA 4492), Université du Littoral-Côte d’Opale, 145, Avenue Maurice Schumann,
MREI 1, 59140, Dunkerque, France
Eric Lichtfouse INRA, UMR Agroécologie, BP 86510 21065, Dijon Cedex, France,
Eric.Lichtfouse@dijon.inra.fr
Shou-Qing Liu School of Chemistry and Bioengineering, Suzhou University of
Science and Technology, Suzhou 215009, China, shouqing_liu@hotmail.com
Isabelle Mallard Unité de Chimie Environnementale et Interactions sur le Vivant
(EA 4492), Université du Littoral-Côte d’Opale, 145, Avenue Maurice Schumann,
MREI 1, 59140, Dunkerque, France
Abdul Rahman Mohamed School of Chemical Engineering, Engineering Campus,
Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S., Pulau
Pinang, Malaysia
Eric Monflier Unité de Catalyse et de Chimie du solide (UMR 8181) Université
d’Artois, Faculté Jean Perrin Rue Jean Souvraz - SP 18, 62307 Lens Cedex
P.R. Anupama Nair Department of Marine Biology, Microbiology and Bio-
chemistry, Cochin University of Science and Technology, Cochin,Kerala 682 016,
India, anupama.pr@gmail.com
Yit Thai Ong School of Chemical Engineering, Engineering Campus, Universiti
Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S., Pulau Pinang, Malaysia
Greta Patrinoiu Coordination and Supramolecular Chemistry Laboratory, Institute
of Physical Chemistry “Ilie Murgulescu”, Romanian Academy, Splaiul Independentei
202, 060021 Bucharest, Romania
Anne Ponchel Unité de Catalyse et de Chimie du solide (UMR 8181) Université
d’Artois, Faculté Jean Perrin, Rue Jean Souvraz - SP 18, 62307 Lens Cedex
Mathias Ricking Department of Earth Sciences, Hydrogeology, Free University of
Berlin, Malteserstr. 74-100, 122249 Berlin, Germany, ricking@zedat.fu-berlin.de
Contributors xix

Didier Robert Equipe ‘Photocatalyse et Nanostructures, LMSPC-CNRS-UMR

7515 et ELCLASS, European Laboratory for Catalysis and, Surface Sciences,
Antenne de Saint-Avold UPV, Metz Rue Victor Demange, 57500, Saint-Avold,
France, drobert@univ-metz.fr
K.K. Satpathy Environmental and Industrial Safety Section, Safety Group, Indira
Gandhi Centre for Atomic Research (IGCAR), Kalpakkam 603102, Tamil Nadu,
India, satpathy@igcar.gov.in
Santosh Kumar Sarkar Department of Marine Science, University of
Calcutta, 35 Ballygunge Circular Road, Calcutta, West Bengal 700 019, India,
sarkar.santosh@gmail.com; sarkar22@yahoo.com
Jan Schwarzbauer Laboratory for Organic-geochemical Analysis, Institute of
Geology and Geochemistry of Petroleum and Coal, RWTH Aachen University,
Lochnerstr. 4-20, 52056 Aachen, Germany, schwarzbauer@lek.rwth-aachen.de
Anuradha Shukla Traffic Planning and Environment Division, Central Road
Research Institute (CSIR), New Delhi 110020, India
Ana R. Stankovic Faculty of Technology and Metallurgy, University of Belgrade,
Karnegijeva 4, 11 000 Belgrade, Serbia, ana.r.stankovic@gmail.com
Slavka Stankovic Faculty of Technology and Metallurgy, University of Belgrade,
Karnegijeva 4, 11 000 Belgrade, Serbia, slavka@tmf.bg.ac.rs
C.H. Sujatha Department of Chemical Oceanography, Cochin University of
Science and Technology, Cochin 682 016, Kerala, India, drchsujatha@yahoo.com
Soon Huat Tan School of Chemical Engineering, Engineering Campus, Universiti
Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S., Pulau Pinang,
Malaysia, chshtan@eng.usm.my
Chin Wei Tan School of Chemical Engineering, Engineering Campus, Universiti
Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S., Pulau Pinang,
Malaysia
Kok Hong Tan School of Chemical Engineering, Engineering Campus, Universiti
Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S., Pulau Pinang, Malaysia
Alina Tirsoaga Physical Chemistry Department, University of Bucharest, Bd.
Elisabeta 4-12, 030018, Bucharest, Romania
Diana Visinescu Coordination and Supramolecular Chemistry Laboratory, Institute
of Physical Chemistry “Ilie Murgulescu”, Romanian Academy, Splaiul Independentei
202, 060021 Bucharest, Romania
Sharif Hussein Sharif Zein School of Chemical Engineering, Engineering
Campus, Universiti Sains Malaysia, Seri Ampangan, 14300 Nibong Tebal, S.P.S.,
Pulau Pinang, Malaysia
 Part I
Nanotechnology
Chapter 1
Carbon Nanotubes Applications: Solar and Fuel
Cells, Hydrogen Storage, Lithium Batteries,
Supercapacitors, Nanocomposites, Gas,
Pathogens, Dyes, Heavy Metals and Pesticides

Chin Wei Tan, Kok Hong Tan, Yit Thai Ong, Abdul Rahman Mohamed,
Sharif Hussein Sharif Zein, and Soon Huat Tan

Contents
List of Abbreviations ............................................................................................................... 4
1.1 Introduction ..................................................................................................................... 5
1.2 Carbon Nanotubes in Energy Conversion and Storage ................................................... 12
1.2.1 Solar Cells............................................................................................................ 12
1.2.2 Fuel Cells ............................................................................................................. 16
1.2.3 Hydrogen Storage ................................................................................................ 18
1.2.4 Lithium Ion Batteries ........................................................................................... 20
1.2.5 Electrochemical Supercapacitors ......................................................................... 22
1.3 Carbon Nanotubes in Environmental Monitoring and Wastewater Treatment ................ 24
1.3.1 Gas Sensors.......................................................................................................... 24
1.3.2 Pathogens ............................................................................................................. 27
1.3.3 Dyes ..................................................................................................................... 28
1.3.4 Heavy Metals ....................................................................................................... 29
1.3.5 Pesticides ............................................................................................................. 32
1.4 Carbon Nanotubes in Green Nanocomposites Design .................................................... 33
1.5 Conclusion ....................................................................................................................... 35
References ................................................................................................................................ 37

Abstract Energy and environment are major global issues inducing environmental
pollution. Energy generation from conventional fossil fuels has been identified as
the main culprit of environmental degradation from global warming effects, in
addition to environmental pollution which arises from rapid industrialization and
agricultural development. In order to address these issues, nanotechnology plays an
essential role in revolutionizing the applications for energy conversion and storage,
environmental monitoring, as well as green engineering of environmental friendly

C.W. Tan • K.H. Tan • Y.T. Ong • A.R. Mohamed • S.H.S. Zein • S.H. Tan (*)
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia,
Seri Ampangan, 14300 Nibong Tebal, S.P.S., Pulau Pinang, Malaysia
e-mail: chshtan@eng.usm.my

E. Lichtfouse et al. (eds.), Environmental Chemistry for a Sustainable World: 3

Volume 1: Nanotechnology and Health Risk, DOI 10.1007/978-94-007-2442-6_1,
© Springer Science+Business Media B.V. 2012
4 C.W. Tan et al.

materials. Carbon nanotubes and their hybrid nanocomposites have received immense
research attention for their potential applications in various fields due to their
unique structural, electronic, and mechanical properties. Here, we review the appli-
cations of carbon nanotubes (i) in energy conversion and storage as in solar cells,
fuel cells, hydrogen storage, lithium ion batteries, and electrochemical supercapaci-
tors, (ii) in environmental monitoring and wastewater treatment as in the detection
and removal of gas pollutants, pathogens, dyes, heavy metals, and pesticides, and
(iii) in green nanocomposite design. Integration of carbon nanotubes in solar cells
and fuel cells has increased the energy conversion efficiency of these energy conver-
sion applications, which serve as the future sustainable energy sources. Carbon
nanotubes doped with metal hydrides show high hydrogen storage capacity of
around 6 wt% as a potential hydrogen storage medium. Carbon nanotubes nano-
composites have exhibited high energy capacity in lithium ion batteries and high
specific capacitance in electrochemical supercapacitors, in addition to excellent
cycle stability. High sensitivity and selectivity towards the detection of environmen-
tal pollutants is demonstrated by carbon nanotubes based sensors, as well as the
anticipated potentials of carbon nanotubes as adsorbent to remove environmental
pollutants, which show high adsorption capacity and good regeneration capability.
Carbon nanotubes are employed as reinforcement material in green nanocompos-
ites, which is advantageous in supplying the desired properties, in addition to the
biodegradability. This paper presents an overview of the advantages imparted by
carbon nanotubes in electrochemical devices of energy applications and green nano-
composites, as well as nanosensor and adsorbent for environmental protection.

Keywords Carbon nanotubes • Energy • Environmental monitoring • Wastewater

• Biotechnology • Nanocomposites

List of Abbreviations

CNTs Carbon Nanotubes

CV Cyclic Voltammetry
DMFC Direct Methanol Fuel Cell
DSSC Dye-Sensitized Solar Cell
ITO Indium-Tin Oxide
MEA Membrane Electrode Assembly
MWCNTs Multi-Walled Carbon Nanotubes
OTE Optically Transparent Electrode
PEMFC Polymer Electrolyte Membrane Fuel Cell
Pt Platinum
QDSC Quantum Dot-Sensitized Solar Cell
Ru(II) Ruthenium Metalorganic Dye
SnO2 Tin Oxide
SWCNTs Single-Walled Carbon Nanotubes
1 Carbon Nanotubes Applications: Solar and Fuel Cells, H2 Storage, Li Batteries... 5

TiO2 Titanium Dioxide

VXC72R Vulcan XC72R
WO3 Tungsten Oxide

1.1 Introduction

Energy and environment issues have been the major global concerns in this twenty-
first century, and they are both on the prioritized list of the top ten problems facing
humanity (Smalley 2005). Undeniably, conventional fossil fuels, such as oil, gas,
and coal have contributed to the energy prosperity in the past century till present
days, but their overwhelming utilization has resulted in their depletion and exhaus-
tion. Furthermore, the combustion of fossil fuels has been identified as the major
cause of increasing atmospheric levels of greenhouse gases, which contribute to the
global warming effects, such as abnormal climate change, increasing rate of natural
disasters and ultimately, environmental degradation. Since the age of industrial rev-
olution, environmental pollution issues have been greatly associated with the rapid
growth in energy demand and production, industrialization and agricultural devel-
opment. The main anthropogenic sources of pollutants are derived from industrial
activities and agricultural activities, such as combustion of fossil fuels, metallurgi-
cal activities, transportation, livestock farming, application of pesticides and herbi-
cides (Bashkin 2003). The environmental pollution of air, water, and soil has resulted
in the degradation of our environmental quality and ecosystem health, giving rise to
the human health concerns caused by pollutants toxicity. In order to enable future
global energy prosperity and preservation of environmental quality, intensive efforts
have been invested on the development of technology to solve the energy and envi-
ronment problems. Recently, nanotechnology has been the field of interest, which
promises in introducing scientific breakthroughs and revolutionary developments
for addressing the energy and environment issues.
Nanotechnology involves the study, manipulation, creation and use of materials,
devices and systems typically with dimensions smaller than 100 nm (Chen et al.
2004). It is based on the fact that some very small structures usually have new
properties and behaviour that are not displayed by the bulk matter with the same
composition. Carbon nanotubes (CNTs) were discovered in 1991 by the Japanese
electron microscopist Sumio Iijima who was studying the material deposited on
the cathode during the arc-evaporation synthesis of fullerenes (Iijima 1991). With
the unique electronic, chemical, mechanical, and structural properties of CNTs,
they are one of the most commonly used building blocks in nanotechnology and
therefore, receiving intense investigation towards the development of their applica-
tion. They represent one of the best examples of novel nanostructures derived by
bottom-up chemical synthesis approaches. They are built from sp2 carbon units in
hexagonal networks or benzene-type hexagonal rings of carbon atoms, as in a gra-
phene sheet (Merkoçi 2006). They can be essentially thought of as a rolled-up
tubular shell of graphene sheet.
6 C.W. Tan et al.

Fig. 1.1 Schematic diagram of the hexagonal honeycomb structure of a graphene sheet and
formation of single-walled carbon nanotubes by rolling the graphene sheet along the lattice vector
AA¢. The chiral vector is defined as Ch = na1 + ma2 which connects two crystallographically
equivalent sites, A and A¢ on a graphene sheet, whereas the chiral angle is taken with respect to the
zigzag axis (n,0). In the diagram: n = 5, m = 3, thus the chirality of the nanotube is (5,3) or
Ch = 5a1 + 3a2 (Charlier 2002). Abbreviations: Ch chiral vector, q chiral angle, A and A¢ crystal-
lographic sites, a1 and a2 unit vectors of hexagonal honeycomb lattice

CNTs can be classified as either single-walled carbon nanotubes (SWCNTs) or

multi-walled carbon nanotubes (MWCNTs). SWCNT is formed by rolling a sheet
of graphene into a cylinder and capped by hemispherical ends, which is a result of
pentagon inclusion in the hexagonal carbon network of the nanotube wall during the
growth process. The diameter and chirality are the key parameters of CNTs, which
are determined by the (n,m) indices in the graphene plane. The ways to roll gra-
phene into tubes are mathematically defined by the chiral vector (Ch) and chiral
angle (q) as illustrated in Fig. 1.1. The chiral vector is defined as Ch = na1 + ma2
where n and m are the integers of the chiral vector considering the unit vectors a1
and a2, whereas the chiral angle is taken with respect to the zigzag axis (n,0). The
relation between n and m defines three categories of CNTs, which are armchair,
zigzag and chiral types of CNTs (Fig. 1.2a). The diameter of SWCNTs is around
0.4–3 nm and several mm in length (Balasubramanian and Burghard 2005).
MWCNT is a stack of graphene sheets rolled up in concentric cylinders
(Fig. 1.2b). The diameters of MWCNTs are in between 2 and 25 nm, and the dis-
tance between sheets or inter layer spacing is about 0.34 nm (Ajayan 1999). The
walls of each layer of MWCNTs are parallel to the central axis, and therefore it is
called concentric MWCNTs. Some other inner textures may be found in MWCNTs,
1 Carbon Nanotubes Applications: Solar and Fuel Cells, H2 Storage, Li Batteries... 7

Fig. 1.2 Schematic illustration of (a) three categories of single-walled carbon nanotubes defined
by its chirality, from left to right: armchair, zigzag, and chiral (Sloan et al. 2002) and (b) Multi-
walled carbon nanotubes (Balasubramanian and Burghard 2005)

such as the herringbone texture and bamboo texture (Rodriguez et al. 1995). The
herringbone texture, in which the graphene make an angle with respect to the nano-
tube axis and the angle varies upon the processing conditions, is obtained from
process involving catalysts, generally catalyst-enhanced thermal cracking of hydro-
carbons. The bamboo texture is described as the occurrence of limited amount of
graphenes oriented perpendicular to the nanotube axis and it affects both concentric
MWCNTs (Fig. 1.3a), and herringbone MWCNTs (Fig. 1.3b).
Arc-discharge, laser ablation and chemical vapour decomposition are the three
main methods for the synthesis of CNTs (Ando and Iijima 1993; Guo et al. 1995;
Che et al. 1998). In arc-discharge method, CNTs are synthesized through arc-
vaporization of two graphite rod placed end to end, namely anode electrode and
cathode electrode. Laser ablation method involves the sublimation of graphite target
and condensation of laser-vaporized carbon/metal mixtures to form CNTs. As for
chemical vapour decomposition, it involves the catalytic decomposition of a carbon
containing gas and nanotube growth on metal catalyst particles impregnated on a
substrate. Arc-discharge and laser ablation are widely employed for the synthesis of
SWCNTs due to the high process temperature of around 1,200°C, which favours
SWCNTs formation. Chemical vapour decomposition is suited for mass production
of MWCNTs as it is a simple and economic technique at lower process temperature
from 500 to 1,000°C.
Regardless of the synthesis method applied, as-prepared CNTs usually contain a
significant amount of impurities, such as amorphous carbon, carbon nanoparticles,
graphitic debris, catalyst particles and fullerenes (Baughman et al. 2002). These
impurities often interfere with the desired properties of CNTs and impede CNTs for
8 C.W. Tan et al.

Fig. 1.3 High-resolution transmission electron microscopy images of (a) concentric multi-walled
carbon nanotubes with bamboo texture, scale bar 5 nm (Harris 1999) and (b) herringbone multi-
walled carbon nanotubes with bamboo texture, scale bar 50 nm (Saito 1995). The bamboo texture
is described as the occurrence of limited amount of graphenes oriented perpendicular to the
nanotube axis, which forms the internal cap across the central tube

detailed characterizations and advanced applications. Various purification techniques

have been employed for the removal of impurities, which include flocculation,
microfiltration, chromatographic, centrifugation, gas phase oxidation, liquid phase
oxidation, and chemical functionalization (Vairavapandian et al. 2008). Typical
purification process involves combinations of these protocols, in which first stage
gas phase oxidation followed with second stage liquid phase oxidation are widely
employed. Gas phase oxidation is an easy and fairly effective purification step to
eliminate amorphous carbon and carbon nanoparticles (Shi et al. 1999). Subsequent
liquid phase oxidation usually employs an acid treatment, which utilizes a strong
oxidizing agent or acid solution, such as HCl, HNO3, H2SO4 or a mixture of these
acids. The liquid phase oxidation not only removes the catalytic metals together
with some amorphous carbon, but it causes defects and/or shortening of CNTs
(Vaccarini et al. 1999; Chen et al. 1998). The oxidation purification steps introduce
carboxylic groups at defective sites of the open ends and the sidewall of CNTs,
which are beneficial for further functionalization and increased solubility.
CNTs possess a framework structure of sp2 hybridized carbon, therefore making
its sidewall very hydrophobic and enriches p-stacking. These properties allow the
functionalization of CNTs to prepare a wide range of nanotubes coupled with
different types of materials, expanding their application range through novel nano-
devices with new functions and applications. Functionalization of CNTs allows the
unique properties of a nanotube to be coupled to those of other types of materials,
Another random document with
no related content on Scribd:
Title Page of Baskerville’s Virgil, Birmingham, 1757 (8½ × 5⅜ inches)
 Text Page of Baskerville’s Virgil, Birmingham, 1757 (8½ × 5⅜ inches)

The Virgil itself, beyond the interest that exists in its type, shows grace and
dignity in its composition and margins. For the first time we have a type title
(page 247) that shows a printer’s appreciation of its possibilities. Baskerville
affected extreme simplicity, employing no head or tail pieces and no
ornamental initials to accomplish his effects (page 249).
The copy of Baskerville’s Virgil in my library contains a copper-plate
frontispiece. The advertisement which particularly emphasized this feature
excited my curiosity, as no book of Baskerville’s is known to have contained
illustrations. When I secured the copy I found that the frontispiece was a steel
engraving stamped on water-marked paper which indicated its age to be at
least two hundred years earlier than the publication of the book. The owner of
this particular copy had inserted the illustration in re-binding, and it was no
part of the original edition!
The glossy paper referred to in Franklin’s letter was an outcome of
Baskerville’s earlier business experience. It occurred to him that type would
print better upon highly finished paper, and that this finish could be secured
by pressing the regular book paper of the time between heated japan plates
made at his own establishment. Baskerville is entitled to the credit of having
been the first printer to use highly finished paper, and, beyond this, as Dibdin
says of him, “He united, in a singularly happy manner, the elegance of Plantin
with the clearness of the Elzevirs.”

Interest in the Baskerville books, and in fact in all books printed in what is
known as “old-style” type, ceased suddenly with the inexplicable popularity
attained about 1800 by the so-called “modern” face. The characteristics of the
old-style letter are heavy ascending and descending strokes with small serifs,
whereas the modern face accentuates the difference between the light and the
heavy lines, and has more angular serifs. The engraved work of Thomas
Bewick, in England, the publication of the Racine by the Didots, and the
Bodoni volumes in Italy, offered the public an absolute innovation from the
types with which they had been familiar since the invention of printing, and
the new designs leaped into such popular favor that many of the foundries
destroyed the matrices of their old-style faces, believing that the call for them
had forever disappeared. As a matter of fact, it was not until the London
publisher Pickering revived the old-style letter in 1844, that the modern face
had any competition. Since then the two styles have been maintained side by
side.
Thus the second supremacy of France came from a change in public taste
rather than from economic causes. For a time there was a question whether
Bodoni would win the distinction for Italy or the Didots for France, but the
French printers possessed a typographical background that Bodoni lacked, and
in their Racine produced a masterpiece which surpasses any production from
the Bodoni Press. The Didots were not only printers and publishers, but
manufactured paper and invented the process of stereotyping. While Minister
to France, in 1780, Benjamin Franklin visited the Didot establishment, and,
seizing the handle of a press, struck off several copies of a form with such
professional familiarity as to cause astonishment.
“Don’t be surprised,” Franklin exclaimed smiling. “This, you know, is my
real business.”
In 1797, the French Minister of the Interior placed at the disposal of
Pierre Didot l’aîné that portion of the Louvre which had formerly been
occupied by the Imprimerie Royale. Here was begun, and completed in 1801, an
edition of Racine in three volumes that aroused the enthusiasm of booklovers
all over the world, and brought to Pierre Didot the glory of being recognized
as a master-printer worthy to assume the mantle of Robert Étienne. This is the
typographic achievement I would select as the masterpiece of its period.
 DIDOT’S RACINE, Paris, 1801
A Frontispiece
Designed by Prud’hon. Engraved by Marius (12 × 8 inches)
Title Page of Didot’s Racine, Paris, 1801 (12 × 8 inches)
Opening Page of Didot’s Racine, Paris, 1801
Text Page of Didot’s Racine, Paris, 1801
 FIRMIN DIDOT, 1730–1804
From Engraving by Pierre Gustave Eugene Staal (1817–1882)

The large quarto volumes contain nearly five hundred pages each. The
type was designed and cut by Firmin Didot in conjunction with, or possibly in
collaboration with Giambattista Bodoni, of Parma, Italy. So closely do the two
faces match that the similarity of their design could scarcely have been a
coincidence (see page 81). There is a peculiar charm in the unusual length of
the ascending and descending characters; there is a grace in the slender capitals
in spite of the ultra-refinement; there is satisfaction in having the weight of the
Italic letter approach that of the Roman, thus preventing the usual blemish
which the lighter faced Italic gives to an otherwise perfectly balanced page.
The figures, really a cross between the old style and the modern, have a
distinct individuality entirely lost in the so-called “lining” figures which those
who have copied this face in America have introduced as an “improvement.”
The Racine contains magnificent steel engravings, of which one is
reproduced at page 253. The handmade paper is a return to the beautiful
sheets of the fifteenth century, and the presswork—the type just biting into
the paper without leaving an impression on the reverse side—is superbly
characteristic of the best French workmanship. The vellum copies show the
work at its best. The engravings stand out almost as original etchings. The ink
is the densest black I ever saw. Didot succeeded in overcoming the oil in the
vellum without the chalk surface that is given to the Morris vellum, the ink
being so heavy that it is slightly raised. I was particularly interested in this after
my own experiments in printing my humanistic Petrarch on vellum.
At the Exposition of 1801, in Paris, the Racine was proclaimed by a French
jury the “most perfect typographic product of any country and of any age.” Is
this not too high praise? To have equaled the Italian masterpieces of the
fifteenth century would have been enough glory for any printer to claim!

The Racine was a step in the direction of reclaiming typography from the
trade which it had become, but it was left for William Morris to place printing
squarely back among the arts.
 WILLIAM MORRIS, 1834–1896
From Portrait by G. F. Watts, R. A. Painted in 1880
National Portrait Gallery, London

Morris was nearly sixty years of age when he finally settled upon the book
as the medium through which to express his message to the world. The Morris
wall papers, the Morris chair, the Morris end papers, are among his earlier
experiments, all sufficiently unique to perpetuate his name; yet his work as a
printer is what gave him undying glory. The Kelmscott Chaucer is his masterpiece,
and must be included whenever great typographic monuments are named. For
this the decorator-printer cut a smaller size of his Gothic font, secured the co-
operation of Sir Edward Burne-Jones as illustrator, and set himself the task of
designing the initial letters, borders, and decorations. This was in 1892, and for
four years they worked upon it, one delay following another to make Morris
fearful that the work might never be completed.
 SIR EDWARD BURNE-JONES, Bart., 1833–1898
From Photograph at the British Museum

The decoration for the first page was finished in March, 1893. Morris was
entirely satisfied with it, exclaiming, “My eyes! how good it is!” Then he laid
the whole project aside for over a year, while he devoted himself to his
metrical version of Beowulf. In the meantime Burne-Jones was experiencing
great difficulty in having his designs satisfactorily translated onto wood, and
Morris dolefully remarked, after comparing notes with his friend and
collaborator, “We shall be twenty years at this rate in getting it out!”
It was June, 1894, before the great work was fairly under way. “Chaucer
getting on well,” Morris notes in his diary,—“such lovely designs.” At the end
of June he records his expectation of beginning the actual printing within a
month, and that in about three months more all the pictures and nearly all the
borders would be ready for the whole of the Canterbury Tales.
About this time Morris was asked if he would accept the poet-laureateship
of England, made vacant by Tennyson’s death, if offered to him, and he
unhesitatingly declined. His health and strength were noticeably failing, yet at
the beginning of 1895, less than two years before his death, he was completely
submerged by multifarious occupations. Two presses were running upon the
Chaucer and still a third upon smaller books. He was designing new paper
hangings and writing new romances; he was collaborating in the translation of
Heimskringla and was supervising its production for the Saga Library; he was
engaged in getting together his splendid collection of thirteenth- and
fourteenth-century illuminated manuscripts.
It was not all smooth sailing with the Chaucer. In 1895 Morris discovered
that many of the sheets had become discolored by some unfortunate
ingredient of the ink, but to his immense relief he succeeded in removing the
yellow stains by bleaching. “The check of the Chaucer,” he writes, “flattens life
for me somewhat, but I am going hard into the matter, and in about a
fortnight hope to know the worst of it.”
In December the Chaucer was sufficiently near completion to encourage
him to design a binding for it. Even here he found another difficulty. “Leather
is not good now,” he complained; “what used to take nine months to cure is
now done in three. They used to say ‘What’s longest in the tanyard stays least
time in the market,’ but that no longer holds good. People don’t know how to
buy now; they’ll take anything.”
Morris’ anxiety over the Chaucer increased as it came nearer to completion.
“I’d like it finished tomorrow!” he exclaimed. “Every day beyond tomorrow
that it isn’t done is one too many.” To a visitor, looking through the printed
sheets in his library, who remarked upon the added beauty of those sheets that
follow the Canterbury Tales, where the picture pages face one another in pairs,
Morris exclaimed in alarm, “Now don’t you go saying that to Burne-Jones or
he’ll be wanting to do the first part over again; and the worst of that would be
that he’d want to do all the rest over again because the other would be so
much better, and then we should never get done, but be always going round
and round in a circle.”
The daily progress of the work upon the Chaucer was the one interest that
sustained his waning energies. The last three blocks were brought to him on
March 21, 1896. The Easter holidays almost killed him. “Four mouldy Sundays
in a mouldy row,” he writes in his diary. “The press shut and Chaucer at a
standstill.”
On May 6 all the picture sheets were printed and the block for the title
page was submitted for Morris’ approval, the final printing being completed
two days later. On June 2 the first two bound copies were delivered to him,
one of which he immediately sent to Burne-Jones, the other he placed in his
own library.
Thus the Kelmscott Chaucer came to completion. Four months later William
Morris was dead. The Chaucer had been nearly five years in preparation and
three and a half years in execution. The printing alone had consumed a year
and nine months. The volumes contain, besides eighty-seven illustrations by
Burne-Jones, a full-page woodcut title, fourteen large borders, eighteen frames
for pictures, and twenty-six large initial words, all designed by Morris, together
with the smaller initials and the design for binding, which was in white pigskin
with silver clasps, executed by Douglas Cockerell.
 Text Page of Kelmscott Chaucer, London, 1896 (15 × 10¼ inches)

I have never felt that the Kelmscott volumes were books at all, but were,
rather, supreme examples of a master-decorator’s taste and skill. After all, a
book is made to read, and the Kelmscott Chaucer is made to be looked at. The
principles which should control the design of the ideal book as laid down by
William Morris cannot be improved upon, but when he undertook to put
them into execution he found himself so wholly under the control of his
decorating tendencies that he departed far from his text. William Morris’ work
is far greater than is shown in the volumes he printed. He awoke throughout
the world an interest in printing as an art beyond what any other man has ever
accomplished, the results of which have been a vital factor in bringing modern
bookmaking to its present high estate.

It remained for T. J. Cobden-Sanderson, Morris’ friend, admirer, and

disciple, to put Morris’ principles into operation at the Doves Press, London,
supplemented by Emery Walker, who designed the Doves type,—to me the
most beautiful type face in existence. Cobden-Sanderson, undisturbed by
counter interests, plodded along, producing volumes into which he translated
Morris’ ideals far more consistently than did Morris himself. “The Book
Beautiful,” Cobden-Sanderson wrote in his little masterpiece, The Ideal Book,
“is a composite thing made up of many parts and may be made beautiful by
the beauty of each of its parts—its literary content, its material or materials, its
writing or printing, its illumination or illustration, its binding and decoration—
of each of its parts in subordination to the whole which collectively they
constitute; or it may be made beautiful by the supreme beauty of one or more
of its parts, all the other parts subordinating or even effacing themselves for
the sake of this one or more, and each in turn being capable of playing this
supreme part and each in its own peculiar and characteristic way. On the other
hand each contributory craft may usurp the functions of the rest and of the
whole, and growing beautiful beyond all bounds ruin for its own the common
cause.”
The Doves Bible is Cobden-Sanderson’s masterpiece, and one turns to it
with relief after the riotous beauty of the Morris pages. It is printed
throughout in one size of type with no leads between the lines and with no
paragraphs, the divisions being indicated by heavy paragraph marks. The only
decorative feature of any description consists of exceedingly graceful initial
letters at the beginning of each new book. The type is based flatly upon
Jenson’s Roman face, and exactly answers Morris’ definition of the type ideal,
“Pure in form, severe, without needless excrescences, solid without the
thickening and thinning of the lines, and not compressed laterally.” The
presswork is superb.
Title Page of Doves Bible, London, 1905 (8 × 6 inches)
 Text Page of Doves Bible, London, 1905 (8 × 6 inches)

Surely no form of bibliomania can yield greater rewards in return for study
and perseverance. The great typographical monuments, dating from 1456 to
1905, have given me a composite picture of man’s successful struggle to free
himself from the bonds of ignorance. I have mingled with Lorenzo the
Magnificent and with the oppressed people of Florence; I have been a part of
François I’s sumptuous Court, and have seen the anxious faces of the clerical
faction as they read the writing on the wall; I have listened to the preaching of
Luther, and have heard the Spanish guns bombarding Antwerp; I have stood
with the brave defenders of Leyden, and have watched the center of learning
find its place in Holland; I have enjoyed Ben Franklin’s participation in the
typographical efforts of Baskerville and Didot; I have received the inspiration
of seeing William Morris and Cobden-Sanderson put a great art back into its
rightful place. These triumphs of the printing press are far more than books.
They stand as landmarks charting the path of culture and learning through
four marvelous centuries
What volume of the twentieth century and what master-printer shall be
included? That is yet to be determined by the test of retrospect; but the choice
will be more difficult to make. In America and England history is being made
in printing as an art, and the results are full of hopefulness and promise