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Chitosan in
THE PRESERVATION
OF AGRICULTURAL
COMMODITIES
Page left intentionally blank
Chitosan in
THE PRESERVATION
OF AGRICULTURAL
COMMODITIES
Edited by

SILVIA BAUTISTA-BAÑOS
Centro de Desarrollo de Productos Bióticos (CEPROBI),
Instituto Politécnico Nacional, Carretera Yautepec-Jojutla,
San Isidro Yautepec, Morelos, México

GIANFRANCO ROMANAZZI
Department of Agricultural, Food and Environmental
Sciences, Marche Polytechnic University,
Via Brecce Bianche, Ancona, Italy

ANTONIO JIMÉNEZ-APARICIO
Departamento de Biotecnología, Centro de Desarrollo de
Productos Bióticos (CEPROBI), Instituto Politécnico Nacional,
Carretera Yautepec–Jojutla, San Isidro Yautepec, Morelos,
México

Amsterdam • Boston • Heidelberg • London

New York • Oxford • Paris • San Diego
San Francisco • Singapore • Sydney • Tokyo
Academic Press is an imprint of Elsevier
Academic Press is an imprint of Elsevier
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, USA
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK

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Publisher (other than as may be noted herein).

Notices
Knowledge and best practice in this field are constantly changing. As new research and experience
broaden our understanding, changes in research methods, professional practices, or medical treatment
may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in evaluating and
using any information, methods, compounds, or experiments described herein. In using such informa-
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for whom they have a professional responsibility.

To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume
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CONTENTS

List of Contributors xi
Prefacexv

PART 1. Chitosan Obtention and New Materials

Based-Chitosan1
1. Chemical Characteristics and Functional Properties
of Chitosan 3
Jaime Lizardi-Mendoza, Waldo M. Argüelles Monal,
Francisco M. Goycoolea Valencia

Introduction 3
Chitosan: Definition and sources 4
Physicochemical characteristics 5
Functional properties 11
Concluding remarks 22
Acknowledgments 23
References 23

2. New Bioactive Biomaterials Based on Chitosan 33

Elsa Bosquez-Molina, Leonor Zavaleta-Mejía

Introduction 33
Physical and chemical characteristics of chitosan 34
Production of chitooligosaccharides (COS) 35
Functionalized chitosan 37
Nanocomposites 44
Applications of chitosan derivatives in agricultural commodities
and packaging industry 50
Characterization of chitosan derivatives molecules 52
Concluding remarks 56
References 57

v
vi Contents

PART 2. Biological Activity, and Mode of

Action of Chitosan 65
3. Application of Chitosan in Fresh and Minimally
Processed Fruits and Vegetables 67
Susana Patricia Miranda-Castro

Introduction 67
Apple 68
Asparagus 68
Avocado 69
Banana 70
Broccoli 72
Carrot 72
Citrus 74
Dragon fruit (pitaya) 77
Grapes 78
Green beans 81
Guava 81
Jujube 82
Litchi 83
Mango 84
Mushrooms 86
Papaya 87
Peach 90
Pear 91
Plum 92
Pomegranate 93
Potato 93
Radish 94
Rambutan 94
Raspberry 95
Red bell pepper 96
Squash 96
Strawberries 97
Sweet cherry 99
Sweet pepper 100
Tomato 101
Concluding remarks 102
Acknowledgments 104
References 104
 Contents vii

4. Chitosan Protection From Rice Diseases 115

Miguel Ángel Ramírez-Arrebato, Aida Tania Rodríguez-Pedroso,
Silvia Bautista-Baños, Elsa Ventura-Zapata

Introduction 115
Major rice diseases and control methods 115
Antimicrobial activity of chitosan against rice fungal pathogen 117
Induction of rice defense mechanisms by chitosan 119
Chitosan’s protection of rice against diseases under
controlled conditions 120
Prospects and problems involved in using chitosan to protect rice 122
Concluding remarks 122
Acknowledgments 123
References 123

5. Integrated Application of Chitosan Coating with Different

Postharvest Treatments in the Control of Postharvest Decay
and Maintenance of Overall Fruit Quality 127
Dharini Sivakumar, Malick Bill, Lise Korsten, Keith Thompson

Introduction 127
Fruit coatings 128
Properties of chitosan 129
Chitosan in combination with modified atmosphere packaging 130
Chitosan in combination with physical treatments 135
Chitosan in combination with plant derivatives 135
Chitosan in combination with organic polymers 141
Chitosan in combination with organic salts 142
Chitosan in combination with nanocomposites 144
Chitosan in combination with organic acids 144
Chitosan in combination with antagonistic microorganisms 145
Chitosan in combination with ethyl alcohol 146
Chitosan and minimally processed fruit and vegetables 147
Concluding remarks 148
References 148

6. Use of Chitosan to Control Postharvest Decay of Temperate

Fruit: Effectiveness and Mechanisms of Action 155
Gianfranco Romanazzi, Erica Feliziani

Introduction 155
Effects on postharvest decay of fruit 155
viii Contents

Mechanisms of action 166

Concluding remarks 171
References 171

7. Chitosan and Its Derivatives as Active Ingredients

Against Plant Pests and Diseases 179
Mohamed E. I. Badawy, Entsar I. Rabea

Introduction 179
Chemistry and properties of chitosan 180
Biological activity of chitosan against plant diseases and pests 182
Technological applications of chitosan in agricultural diseases
and pest control 195
Proposed mechanisms of chitosan action against plant pests
and diseases 200
Concluding remarks 202
Acknowledgments 202
References 202

8. Prospects for the Use of Chitosan and Other Alternatives

in Ornamental Conservation 221
Laura Leticia Barrera Necha, Silvia Bautista-Baños

Introduction 221
Common phythopathogens of ornamentals 223
Physical alternatives 224
Host plant material resistance 225
Biocontrol 227
Chemical control 229
Alternatives under experimentation 231
Plant growth promotion and effects of plant development 233
Plant extracts and essential oils 234
Concluding remarks 239
Acknowledgments 240
References 240

9. Morphological and Ultrastructural Modifications

of Chitosan-Treated Fungal Phytopathogens 251
Silvia Bautista-Baños, Laura Leticia Barrera Necha, Mónica Hernández-López,
Francisco Rodríguez-González

Introduction 251
Fungus definition 255
 Contents ix

Fungal structures and functions 255

Proposed mechanisms of action of chitosan on fungi 257
In vitro morphological alterations induced by chitosan on fungi 259
In vitro structural alterations induced by chitosan on fungi 259
Cytological changes induced by chitosan in different fungal pathosystems 261
Concluding remarks 269
Acknowledgments 271
References 271

PART 3. Biochemical and Molecular Aspects of Chitosan 277

10. Biochemical Aspects of the Chitin Fungicidal Activity
in Agricultural Uses 279
Cristóbal Lárez Velásquez, Maura Rojas Pirela

Introduction 279
Some mechanisms proposed for the fungicidal activity of chitin 282
Future trends 289
Concluding remarks 293
Acknowledgments 293
References 293

11. Chitosan and Changes in Gene Expression During

Fruit–Pathogen Interaction at Postharvest Stage 299
Porfirio Gutiérrez-Martínez, Alejandra Chacón-López,
Luis Angel Xoca-Orozco, Anelsy Ramos-Guerrero,
Rita Velázquez-Estrada, Selene Aguilera-Aguirre
Introduction 299
Chitosan as a resistance inducer 302
Differential gene expression analysis 304
Concluding remarks 306
Acknowledgments 307
References 307

PART 4. Chitosan Bio-Nanocomposites 313

12. Chitosan-Based Bionanocomposites: Development
and Perspectives in Food and Agricultural Applications 315
Cynthia Nazareth Hernández-Téllez, Maribel Plascencia-Jatomea,
Mario Onofre Cortez-Rocha

Introduction 315
Chitosan 318
x Contents

Methods for obtaining nanoparticulated systems 326

Toxicity of chitosan-based NPs 329
Antimicrobial activity of chitosan-based NPs 331
Chitosan-based nanoparticulated systems loaded with bioactive compounds 333
Concluding remarks 335
Acknowledgments 335
References 336

13. Biological Activity of Chitosan Nanoparticles Against

Pathogenic Fungi and Bacteria 339
María Elena Sotelo-Boyás, Silvia Bautista-Baños,
Zormy N. Correa-Pacheco, Antonio Jiménez-Aparicio,
Dharini Sivakumar

Introduction 339
Potential of nanotechnology in the control of pathogenic fungi
and bacteria 340
Biological activity of chitosan in the control of phytopathogenic fungi 340
Biological activity of chitosan nanoparticles in the control
of phytopathogenic bacteria 342
Biological activity of chitosan nanoparticles against foodborne pathogens 343
Concluding remarks 346
References 347

Index 351
LIST OF CONTRIBUTORS

Selene Aguilera-Aguirre
División de Estudios de Posgrado e Investigación-Alimentos, Instituto Tecnológico de
Tepic, LIIA, Laboratorio de Biotecnología, Lagos del Country, Tepic, Nayarit, México
Waldo M. Argüelles Monal
Grupo de Investigación en Biopolímeros, CTAOA, Centro de Investigación en
Alimentación y Desarrollo AC, Hermosillo, Sonora, México
Mohamed E.I. Badawy
Department of Pesticide Chemistry and Technology, Faculty of Agriculture, Alexandria
University, Alexandria, Egypt
Laura Leticia Barrera Necha
Centro de Desarrollo de Productos Bióticos (CEPROBI), Instituto Politécnico Nacional,
Carretera Yautepec-Jojutla, San Isidro Yautepec, Morelos, México
Silvia Bautista-Baños
Centro de Desarrollo de Productos Bióticos (CEPROBI), Instituto Politécnico Nacional,
Carretera Yautepec-Jojutla, San Isidro Yautepec, Morelos, México
Malick Bill
Postharvest Technology Group, Department of Crop Sciences, Tshwane University of
Technology, Pretoria West, Pretoria, South Africa
Elsa Bosquez-Molina
Departamento de Biotecnología, Universidad Autónoma Metropolitana-Iztapalapa
Vicentina, Iztapalapa, Mexico City, México
Alejandra Chacón-López
División de Estudios de Posgrado e Investigación-Alimentos, Instituto Tecnológico de
Tepic, LIIA, Laboratorio de Biotecnología, Lagos del Country, Tepic, Nayarit, México
Zormy N. Correa-Pacheco
Centro de Desarrollo de Productos Bióticos (CEPROBI), Instituto Politécnico Nacional,
Carreterra Yautepec–Jojutla, San Isidro Yautepec, Morelos, México
Mario Onofre Cortez-Rocha
Departamento de Investigación y Posgrado en Alimentos, Universidad de Sonora,
Hermosillo, Sonora, México
Erica Feliziani
Department of Agricultural, Food and Environmental Sciences, Marche Polytechnic
University,Via Brecce Bianche, Ancona, Italy
Francisco M. Goycoolea Valencia
Grupo de Investigación en Biopolímeros, CTAOA, Centro de Investigación en
Alimentación y Desarrollo AC, Hermosillo, Sonora, México

xi
xii List of Contributors

Porfirio Gutiérrez-Martínez
División de Estudios de Posgrado e Investigación-Alimentos, Instituto Tecnológico de
Tepic, LIIA, Laboratorio de Biotecnología, Lagos del Country, Tepic, Nayarit, México
Mónica Hernández-López
Centro de Desarrollo de Productos Bióticos (CEPROBI), Instituto Politécnico Nacional,
Carretera Yautepec-Jojutla, San Isidro Yautepec, Morelos, México
Cynthia Nazareth Hernández-Téllez
Departamento de Investigación y Posgrado en Alimentos, Universidad de Sonora,
Hermosillo, Sonora, México
Antonio Jiménez-Aparicio
Departamento de Biotecnología, Centro de Desarrollo de Productos Bióticos (CEPROBI),
Instituto Politécnico Nacional, Carretera Yautepec–Jojutla, San Isidro Yautepec, Morelos,
México
Lise Korsten
Plant Sciences and Crop Sciences, University of Pretoria, Hillcrest, Pretoria, South Africa
Jaime Lizardi-Mendoza
Grupo de Investigación en Biopolímeros, CTAOA, Centro de Investigación en
Alimentación y Desarrollo AC, Hermosillo, Sonora, México
Susana Patricia Miranda-Castro
Departamento de Ciencias Biológicas, Facultad de Estudios Superiores Cuautitlan,
Laboratorio de Biotecnología, UNAM, Estado de México, México
Maura Rojas Pirela
Departamento de Biología, Facultad de Ciencias, Laboratorio de Enzimología de Parásitos,
Universidad de Los Andes, Mérida,Venezuela
Maribel Plascencia-Jatomea
Departamento de Investigación y Posgrado en Alimentos, Universidad de Sonora,
Hermosillo, Sonora, México
Entsar I. Rabea
Department of Plant Protection, Faculty of Agriculture, Damanhour University,
Damanhour, Egypt
Miguel Ángel Ramírez-Arrebato
UCTB Los Palacios, Instituto Nacional de Ciencias Agrícolas (INCA), Los Palacios, Pinar
del Río, Cuba
Anelsy Ramos-Guerrero
División de Estudios de Posgrado e Investigación-Alimentos, Instituto Tecnológico de
Tepic, LIIA, Lagos del Country, Tepic, Nayarit, México
Francisco Rodríguez-González
Departamento de Biotecnología, Centro de Desarrollo de Productos Bióticos (CEPROBI),
Instituto Politécnico Nacional, Carretera Yautepec-Jojutla, San Isidro Yautepec, Morelos,
México
 List of Contributors xiii

Aida Tania Rodríguez-Pedroso

UCTB Los Palacios, Instituto Nacional de Ciencias Agrícolas (INCA), Carretera La
Francia, Los Palacios, Pinar del Río, Cuba
Gianfranco Romanazzi
Department of Agricultural, Food and Environmental Sciences, Marche Polytechnic
University,Via Brecce Bianche, Ancona, Italy
Dharini Sivakumar
Department of Crop Sciences, Postharvest Technology Group, Tshwane University of
Technology, Pretoria West, Pretoria, South Africa
María Elena Sotelo-Boyás
Centro de Desarrollo de Productos Bióticos (CEPROBI), Instituto Politécnico Nacional,
Carretera Yautepec-Jojutla, San Isidro Yautepec, Morelos, México
Keith Thompson
Department of Crop Sciences, Postharvest Technology Group, Tshwane University of
Technology, Pretoria West, South Africa; Cranfield University, Cranfield, Bedford, UK
Cristóbal Lárez Velásquez
Grupo de Polímeros, Departamento de Química, Facultad de Ciencias, Universidad de Los
Andes, Mérida,Venezuela
Rita Velázquez-Estrada
División de Estudios de Posgrado e Investigación-Alimentos, Instituto Tecnológico de
Tepic, LIIA, Laboratorio de Biotecnología, Lagos del Country, Tepic, Nayarit, México
Elsa Ventura-Zapata
Departamento de Biotecnología, Centro de Desarrollo de Productos Bióticos (CEPROBI),
Instituto Politécnico Nacional, Carretera Yautepec-Jojutla, San Isidro Yautepec, Morelos,
México
Luis Angel Xoca-Orozco
División de Estudios de Posgrado e Investigación-Alimentos, Instituto Tecnológico de
Tepic, LIIA, Laboratorio de Biotecnología, Lagos del Country, Tepic, Nayarit, México
Leonor Zavaleta-Mejía
Departamento de Ingeniería Química y Bioquímica, Instituto Tecnológico de Zacatepec,
Zacatepec de Hidalgo, Zacatepec, Morelos, México
Page left intentionally blank
PREFACE

In June 2014, the First International Meeting, with the title Chitosan and Its
Applications on the Preservation of Agricultural Commodities was held in Morelos,
México. This outstanding event brought together relevant scientists and
students working with chitosan in the fields of agriculture from different
countries including Cuba, Italy, South Africa, Venezuela, and México. This
meeting made clear the necessity of summarizing and updating available
information on this compound associated within agriculture areas, specifi-
cally in dealing with its application for the conservation of horticultural
commodities.
Regarding this compound it is important to note that over the past de-
cade, chitosan (the deacetylated form of chitin) polysaccharides have gained
enormous importance in diverse scientific disciplines (e.g., pharmaceutical
and biomedical areas), where literature has been systematically published.
Furthermore, in these two disciplines, applications of chitosan now include
among others, nutrition supplements, drug delivery, gene therapy, tissue en-
gineering, and wound healing. Fortunately, advancements have shown posi-
tive results also in the area of agriculture. The presence of amino groups
(–NH2) in its chemical structure has resulted in chitosan exhibiting unique
and ideal properties in different agricultural systems, including food con-
servation and food security through development of biodegradable edible
coatings and films containing natural antimicrobials. Chitosan has also been
integrated into programs of biological disease control due to its document-
ed antimicrobial properties for controlling pathogenic microorganisms in
various horticultural commodities. It has elicitor properties that enhance
the natural defenses of fruits, vegetables, and grains. Chitosan is also be-
ing considered in microdevices to be integrated in “intelligent” and active
packing for extending fruit and vegetable shelf life.
Chitosan can be extracted from diverse marine organisms, insects, and
fungi. It has been considered a biodegradable and biocompatible material,
not associated with toxicity or side effects. Presently, the use of chitosan has
been technologically justified in sustainable agriculture programs because
it raises no public health and safety concerns. In the fresh produce indus-
try, this compound is safe for the consumer and the environment, and it
has been approved by the US Food and Drug Administration (FDA) as a
“generally recognized as safe” (GRAS) food additive. Likewise, regulation

xv
xvi Preface

EU 2014/563 included chitosan chloride as the first member of a basic

substance list of plant protection products (planned with Regulation EU
2009/1107).
This specialized book on chitosan includes the following sections:
The first section, Chitosan Obtention and New Materials-Based Chitosan,
explores the close relationship between the chemical characteristics of chi-
tosan with its main functional properties, and the current functional chito-
san derivatives. It explains the relationship between chitosan structure and
its modifications and the specific properties in the final product as well as
its potential of application, particularly in the agricultural and horticultural
food sectors.The second section, Biological Activity, and Mode of Action of Chi-
tosan, examines the effects of novel integrated applications of chitosan coat-
ings, alone and in combination with other technologies such as modified
atmosphere packaging, plant derivatives, plant gums, physical treatments,
organic polymers, organic salts, and antagonist microorganisms in the pres-
ervation of fresh fruits, vegetables, and grains, including minimally processed
products.The enzymatic and microscopic defense mechanisms against plant
diseases and pests following chitosan application are also considered. The
third section, Biochemical and Molecular Aspects of Chitosan, deals with the
main mechanisms proposed to explain the beneficial effects observed when
chitinous materials that are employed to control fungal diseases in plants.
These effects include the occurrence of a fertilizer effect, indirect inhibition
of the pathogens via their decomposition by-products, stimulating/sup-
porting growth of profitable microorganisms, and elicitor activity of chitin.
Likewise, studies of the gene expression during the chitosan–Colletotrichum–
avocado interaction are presented. The fourth section, Chitosan Bionanocom-
posites, gives insight on the use of chitosan nanocomposites in biological
models associated with fruit and vegetable conservation. Aspects related to
the development of chitosan bionanocompounds, main nanoparticle ob-
taining methods, and environmental implications associated with the use of
nanomaterials in the agricultural area were also considered.
The contributors to this book are nationally and internationally rec-
ognized scientists with wide experience in the study of different aspects of
chitosan. Throughout recent years they have been active researchers in the
field of chitosan, focusing in different aspects of agriculture and food con-
servation, which is demonstrated by their numerous high-impact publica-
tions on chitosan properties and applications. We editors acknowledge and
thank their enthusiastic interest in participating in the writing of this book.
 Preface xvii

We are also deeply grateful for the continuous support and encourage-
ment of this idea from the Elsevier team: Patricia Osborne (Acquisitions
Editor), Jackie Truesdell (Editorial Project Manager), and Susan Li (Produc-
tion Department).

The Editors
Silvia Bautista-Baños
Gianfranco Romanazzi
Antonio Jiménez-Aparicio
Page left intentionally blank
PART 1

Chitosan Obtention
and New Materials
Based-Chitosan
1. Chemical Characteristics and Functional Properties of Chitosan 3
2. New Bioactive Biomaterials Based on Chitosan 33

1
Page left intentionally blank
CHAPTER 1

Chemical Characteristics and

Functional Properties of Chitosan
Jaime Lizardi-Mendoza, Waldo M. Argüelles Monal,
Francisco M. Goycoolea Valencia

INTRODUCTION
Chitin is an aminated polysaccharide biosynthesized in several invertebrate
animal species. It is a main compound of the exoskeleton of arthropods, the
most abundant animal phyla that include insects and crustaceans. The pres-
ence of chitin in some microorganisms such as bacteria, fungi, protozoan,
and algae species has also been reported [1]. Chitin is considered one of the
most abundant biopolymers and is regarded as one of the substances with
highest production and degradation rate in the biosphere. Therefore, chitin
plays an important role in the biogeochemical cycles of carbon and nitro-
gen, mainly in aquatic ecosystems [1,2].
Despite chitin being almost as abundant as cellulose and sharing several
chemical and functional features with it, chitin applications are ­restricted
to a few specialized fields. There are several reasons for this; one is that the
natural structures of chitin that could be easily used are scarce (in contrast
with cellulose structures such as wood or cotton). Other reasons are the
difficulties in obtaining stable chitin solutions or the product variability
associated with the inherent diversity of the sources and extraction proce-
dures. Therefore, most of the chitin production is dedicated to obtain chi-
tosan, which is a deacetylated derivative. After the deacetylation ­process,
the resulting chitosan has diverse functional groups: some capable of being
ionized, the amino moieties, and also the remaining acetamide groups that
are prone to form hydrophobic associations. This chemical characteristic
of chitosan has influence in many functional properties of this molecule
(i.e., at acid pH values, the amino groups become cationic, promoting the
dissolution of chitosan). Also the polycationic character of chitosan al-
lows it to interact with diverse types of molecules. This, together with its
structural capacities, biocompatibility, and other properties, make chitosan
attractive for producing functional materials applicable in several fields.

Chitosan in the Preservation of Agricultural Commodities Copyright © 2016 Elsevier Inc.

http://dx.doi.org/10.1016/B978-0-12-802735-6.00001-X All rights reserved. 3
4 Chitosan in the Preservation of Agricultural Commodities

CHITOSAN: DEFINITION AND SOURCES

Chitosan is the term used to denominate the polymer of glucosamine and
N-acetyl glucosamine where the deacetylated units are present in major
proportion or their distribution in the polymer chain is such that allows it
to be dissolved in aqueous diluted acid solutions. A distinctive feature of the
chemical structure of chitosan (Figure 1.1) is the predominant presence of
units with amino groups that can be ionized.These groups become cationic
in acidic media promoting the chitosan dissolution and polyelectrolyte be-
havior in solution.
In 1859, Rouget obtained an acid soluble fraction of chitin after boiling
it in a concentrated potassium hydroxide solution [3].This is considered the
first scientific report of chitosan. Subsequently, the synthesis and occurrence
of chitosan in diverse organisms, mainly fungi, was proved. However, its nat-
ural abundance is minimal compared with chitin abundance. Hence, most
of the chitosan is produced by thermochemical deacetylation of chitin.
Multiple procedures have been proposed and developed to obtain ­chitosan
and comprehensive reviews on the theme are available [3–5]. Most of the
existing methods to produce chitosan are variations on ­thermo-alkaline
deacetylation of chitin using hydroxides at high temperatures (e.g., >80°C).
The industrial production of chitosan today is based on this type of process.
Chitosan could be also obtained by homogeneous chemical deacetylation
of chitin [6]. Alternatively, biotechnological procedures have been proposed,
including extraction from cultures of selected fungi strains or enzymatic
deacetylation of chitin with limited success [7,8].
Typical chitin deacetylation by a thermo-alkaline procedure is a het-
erogeneous phase reaction, where the process conditions (e.g., starting ma-
terial quality, particle size, reactants mixture ratio, additives, agitation rate,
etc.) have a determinant influence on the characteristics of the produced
­chitosan. Consequently, notable variability on the functional properties of
produced chitosan has been observed [9]. To achieve uniform production
with proper quality control, an accurate monitoring through the entire
process is required. Nowadays, consistent quality values and standardized

Figure 1.1 Chemical Structure of Chitosan. Schematic interpretation of the ­polycationic

state of chitosan (acetylation = 1/7) in acid aqueous solutions.
 Chemical Characteristics and Functional Properties of Chitosan 5

methods to characterize chitosan intended for diverse applications are being

discussed and adopted [9–11].
Homogeneous alkaline deacetylation of chitosan has been also reported
[6,12]. Slow random deacetylation of the chitin molecules takes place in alkali
chitin solutions at room temperature.This method of deacetylation could take
up to 48 h to produce chitosan with DA of less than 10% in a single treatment.
It was demonstrated that chitosan homogeneously obtained with DA around
50% is soluble in distilled water. The random distribution of the deacetylated
units along the polymer chains generates a balance that allows chitosan to be
dissolved in neutral water [6]. An alternative procedure using the chitin swell-
ing in cold alkaline solution has been used to produce homogeneously deacet-
ylated chitosan. In this procedure a mixture of chitin in concentrated NaOH
(10–50% wt) goes through several cycles of freezing and thawing until a chitin
solution is obtained or the chitin particles are swelled. Subsequently it is heated
(up to 100°C) to proceed with the homogenous deacetylation [13,14].
Chitosan is a substantial component of the cell wall of certain fungi,
particularly those belonging to the class Zygomycetes [15–17]. The enzy-
matic deacetylation of chitin has been proved as a synthesis mechanism of
chitosan in fungi.This enzymatic modification plays a role in the regulation
of the interactions of such fungi with plants [7,18,19]. Hence, the two main
biotechnological alternatives to the chemical production of chitosan are
the fermentation of chitosan containing fungal strains and the use of chitin
deacetylases. Considerable research has been conducted in the production
of chitosan by fermentation using different strains and suitable methods for
the extraction of fungal chitosan [15,17,20–22]. Some advantages of this
chitosan production method include obtaining chitosan free of allergenic
animal proteins. The molecular weight and DA of fungal chitosan can be
controlled by varying the fermentation conditions with no demineraliza-
tion. The fermentative production of fungi on cheap biowaste is a continu-
ous and unlimited source of chitosan. Additionally, concurrent extraction of
b-glucans, another bioactive biopolymer, is an extra value-added product
[5,8,15,23]. Despite these advantages, only few documented commercial
ventures are based on biotechnological chitosan production.

PHYSICOCHEMICAL CHARACTERISTICS
The physicochemical characteristics of chitosan are polydispersed due to
the variability associated with sources and production process conditions.
To understand the functional properties of chitosan as a consequence of
6 Chitosan in the Preservation of Agricultural Commodities

measured characteristics such polydispersity should be considered. This also

emphasizes the need for precise and standardized methods to determine
such characteristics, primarily as they apply to the degree of acetylation
and the molecular weight as the main characteristics that influence most of
the properties of chitosan. Other characteristics such as purity, crystallinity,
inorganic matter content, and water content, among others, could be also
relevant in the context of each intended chitosan application [10,11].

Crystalline Structure
In the solid state, chitosan molecules are generally organized in highly
ordered crystallites contained in considerable amorphous regions. There
are two main chitosan crystalline polymorphs [24,25]. One is called the
“tendon chitosan” polymorph, which is a hydrated form and is the most
common. The “annealed polymorph” is an anhydrous crystal form. In both
polymorphs, the crystal cell is formed by two antiparallel chitosan mol-
ecules with a twofold helix conformation stabilized by hydrogen bonds.
Differences among polymorphs arise from the presence of water molecules
between crystal cells stabilizing the structure by multiple hydrogen bonding
[26].Through a heating treatment, it is possible to transform “tendon” form
to the “annealed” form; this transformation is irreversible [26].
For chitosan salts with organic and inorganic acids, up to four crystal-
line polymorphs have been reported. Type “I” salts are mostly anhydrous;
in these crystals the backbone chitosan chains retain the extended twofold
helix of the unmodified chitosan molecule. This conformation of chitosan
is called type I form. Conformational change of chitosan molecule occurred
by salt formations of types II, IIa, and III, where the chains are arranged in
antiparallel helicoids of differentiated fold [24–27].

Degree of Acetylation
The proportion of acetylated and deacetylated groups, or degree of acety-
lation (DA), determines the distinction among chitin and chitosan. Chi-
tin deacetylation reaction progresses by exposing amino groups along the
molecule. The extent and distribution of this modification causes several
changes in the main properties of the molecule. One of the most notori-
ous changes is that, as the amino groups are ionizable, chitosan becomes
polycationic in acidic media. This unusual quality for a biopolymer al-
lows chitosan to be capable of forming solutions and actively interacting
with diverse molecules. Thus, the DA determines most of the properties of
chitosan, including solubility, extent of swelling in water, susceptibility to
 Chemical Characteristics and Functional Properties of Chitosan 7

biodegradation, bioactivity, and biocompatibility among others. Practically,

the DA has influence in all the functional properties of chitosan.
As a fundamental feature in relation to its properties, the accurate deter-
mination of the DA is required for characterization and quality control of
produced chitosan. Several analytical tools have been used to measure DA,
most of which depend on the dissolution of chitosan in aqueous acid sol-
vents.Therefore, a single technique cannot typically be adopted to cover the
full range of DA.The most-used techniques are based in potentiometry, UV
spectroscopy, 1H-NMR and infrared spectroscopy [3,27–30]. The existing
methods have specific advantages and drawbacks. Additionally, DA values
discrepancies are frequent in measurements of the same sample with differ-
ent methods. Hence, the use of an absolute method such as NMR is recom-
mended whenever possible; otherwise, it is necessary indicate precisely the
method and general conditions used.
Absolute methods are those that do not require external standards and
previous calibrations to determine the DA values accurately. The best ex-
ample of this type of method is NMR. Some advantages of NMR are that
it does not need gravimetric measurements; the purity of chitosan does not
need to be known accurately as long as the impurity peaks do not overlap
with the relevant peaks of chitosan; the peaks used for DA determination in
this method are well resolved; and the integration of these peaks is straight-
forward. Also, DA can be calculated using different combinations of peaks
in order to verify that the method is consistent. Due to these advantages,
together with the precision that can be achieved, NMR techniques are
usually employed as the standard to calibrate other methods [27,29,31,32].
High-resolution 1H- and 13C-NMR spectroscopy could be used to estimate
DA of chitosan samples in solution. Solid-state 13C- and 15N-NMR spec-
troscopy could also be used to analyze chitosan samples without the need of
dissolving, although specialized equipment and accessories would need to
be implemented. Liquid phase 1H-NMR is the most suitable method for the
determination of the DA of chitosan. The technique has been proven fast,
precise, reproducible, rugged, robust, and stable. Usually, the determination
of the DA of chitosan by this method is performed in 2% DCl solutions at
70°C [27,29,31,32]. Recently, alternative 1H-NMR operation settings have
been proposed, achieving comparable results more rapidly by using milder
conditions (room temperature) [27,31]. The use of partially deacetylated
chitosan samples is recommended in order to improve the solubility and
obtain high-quality spectra in solution state. It has been demonstrated that
limited depolymerization by nitrous acid treatment does not s­ignificantly
8 Chitosan in the Preservation of Agricultural Commodities

Table 1.1 Absorbance band used to estimate degree of acetylation

Bond Vibration type Wavelength (cm−1) Use

O─H Stretching 3450 Reference

N─H Stretching 3360 Reference
C─H Stretching 2878 Reference
C─H Deformation 1420 Reference
­(pyranose ring)
C─O─C Stretching in glycosidic 1150–1040 Reference
linkage
N─H Bending in secondary 1560 Probe
­amide (amide II)
C═O Stretching in secondary 1660 Probe
acetoamide (amide I)
NH2 Bending in amino group 1590 Probe
C─N Stretching in secondary 1320 Probe
amide (amide III)
CH3 Rocking in acetoamide 1380 Probe
group

modify the estimation of DA or dyad sequence distribution [31]. The DA

could be calculated by several proposed relationships of signal integrals of
the glucose ring and the acetyl group protons [32].
Infrared spectroscopy is one of the most widely used and studied meth-
ods for determining DA, because of its simplicity and availability. The basic
methodology to calculate DA involves the measurement of a probe band
and an internal reference band. Numerous relationships of probe and ref-
erence bands have been proposed to determine the DA of chitin and chi-
tosan samples [28,33]. Table 1.1 includes a number of absorbance bands
used to estimate DA. The quantity of methods proposed suggests that the
FTIR DA determinations depend on sample form, treatment, and calcula-
tion procedure. Therefore, quantitative FTIR analysis should be performed
meticulously, and calibration with respect to an absolute technique is rec-
ommended. Nevertheless, FTIR without calibration has been proved to be
a functional tool to determine differences in DA and crystalline structure
of chitosan [29].

Molecular Weight
The molecular weight of chitosan is a characteristic that has determinant
influence in most of its functional properties [34–36]. Together with the
degree of acetylation, it is the most important chemical characteristics of
 Chemical Characteristics and Functional Properties of Chitosan 9

chitin and chitosan. These characteristics have marked effect on the func-
tional properties of chitosan either in solution or solid state. The molecular
weight has particular influence on the viscoelastic properties of solutions
and hydrated colloidal forms.
As many other natural polymers, the molecular characteristics of chito-
san are polydisperse. This is particularly applicable regarding to the molecu-
lar weight. Chitin presents heterogeneous distribution of molecular weights
as result of constant synthesis and degradation processes in living tissues
and depolymerization during the extraction procedures. In chitosan, the
molecular weight is also result of depolymerization that takes place through
the deacetylation process. Consequently, a given sample is typically a mix-
ture of chitosan molecules of assorted sizes. To describe the heterogeneous
distribution of this fundamental property, several molecular weight averages
are used. Namely, number – average molecular weight (Mn), determined by
osmometry; viscosity – average molecular weight (Mv), estimated by visco-
simetry; weight – average molecular weight (Mw), measured by light scat-
tering (LS); and Z-average molecular weight, obtained by sedimentation
analysis. In a typical distribution curve (Schutlz–Flory distribution), the av-
erage values are related to each other as follows Mn < Mv < Mw < Mz with
an approximate proportion 1:2:3 for Mn:Mw:Mz. The polydispersity index
(PDI) of a sample is defined as Mw divided by Mn and gives an indication
just how wide the distribution could be [37].
Several analytical techniques are available to estimate the average mo-
lecular weight of the chitosan. Most of these chitosan characterization sys-
tems rely on high-efficiency separation techniques, such as size exclusion
chromatography that allows the determination of molecular weight distri-
bution [38]. The viscosimetry and dynamic light scattering techniques are
commonly used to determine the molecular weight of chitosan in diluted
solutions. It is recognized that most accurate information about size, be-
havior, and conformation of a polymer is obtained from solutions in dilute
regime. However, many factors, experimental and relative to the intrinsic of
the studied material, should be considered for a proper determination of the
parameters that describe characteristics of the polymer. Regarding chitosan,
experimental factors that have evident influence on analytical determina-
tions include the characteristics of the solvent system (pH, ionic force, tem-
perature, etc.), solution aging, as well as the purification and fractionation
procedures, among others. All these factors, predominantly the solvent fea-
tures, influence the solute–solvent interactions that determine the polymer
conformation and hydrodynamic volume. The DA and units ­distribution
10 Chitosan in the Preservation of Agricultural Commodities

pattern are examples of intrinsic factors that should be controlled in ana-

lytical determinations. There are numerous reports about chitosan char-
acterization in dilute solutions that have generated valuable conclusions;
however, due to the quantity of possible combinations of factors, unresolved
controversies remain [38–40].
The intrinsic viscosity, [η], is a characteristic parameter of a polymer
under specified solvent and physicochemical conditions (i.e., temperature,
ionic strength, etc.). The [η] is directly proportional to the average molecu-
lar weight of the polymer, accordingly to the Mark–Houwink–­Sakurada
(MHS) equation (Equation 1.1). Several sets of constants (k and exponent a)
reported for chitosan correspond to differences in solvent, ionic strength,
pH, temperature, type, and concentration of cosolvent, as well as molecular
weight and degree of deacetylation of the chitosan used [38,41–44]. There-
fore, it is advisable to report the used set of MHS constants in the molecular
weight estimation of chitosan to avoid ambiguities.

 [η ] = k ⋅ Mαv (1.1)

Techniques of molecular separation such as size exclusion chromatog-

raphy (SEC) have been used to study chitosan solutions corresponding to
narrow molecular weight distributions [45–47]. Determination of the mo-
lecular weight and molecular weight distribution by SEC demands either
proper molecular weight standards with a narrow molecular weight dis-
tribution or the use of appropriate detectors to determine absolute mo-
lecular weight (i.e., light scattering), viscosity, and concentration. Dextrans
and pullulans, flexible and uncharged polysaccharides, have been used as
standards for estimation of molecular weights of rigid polysaccharides such
as chitosan, resulting in overestimated molecular weights. Better results have
been obtained calibrating the SEC system with chitosan fractions with nar-
row molecular weight distribution obtained from preparative SEC. In some
cases, the presence of aggregates could induce the overestimation of the Mw
in light scattering measurements [48]. An adequate solvent system selection
is required to achieve an accurate characterization of the polysaccharide in
solution. The solvent system should reduce the ionic interactions with the
stationary phase, avoiding adsorption, ionic inclusion and exclusion; simi-
larly, it should stabilize the hydrodynamic volume of the polymer [47].
Given the influence of the molecular weight on the properties of
­chitosan, it should be available with a molecular weight range of 3–4 orders
of magnitude in order to satisfy the requirements of its various applications
[49]. Consequently, diverse efforts to manipulate the molecular weight of
 Chemical Characteristics and Functional Properties of Chitosan 11

chitosan have been undertaken in order to control or improve its properties

(e.g., reduce viscosity or enhance water solubility). Typically, the molecular
weight of chitosan is reduced by physical, chemical, or enzymatic hydrolysis.
Physical means provide the added energy needed to break the glycosidic
linkage; for this, thermal, sonic, irradiation, and hydromechanical methods
have been used effectively to depolymerize chitosan [50–52]. Acid, alkaline,
and oxidative reactions have been used to chemically hydrolysate chitosan
[35,49,53]. Alternatively, the use of chitinases and other hydrolytic enzymes
have also been applied to obtain low molecular weight chitosan or oligo-
mers [54–56].

FUNCTIONAL PROPERTIES
The chemical characteristics assembled in chitosan provide it with distinctive
properties. Chitosan is a linear copolymer of close related units; one is the
deacetylated version of the other that displays dissimilar features. ­Acetylated
units, N-acetyl glucosamine, could form hydrogen bonds and hydropho-
bic interactions that stabilize the molecule, providing it with certain rigid-
ity and reinforcing its structural properties. On the other hand, the amino
group of the deacetylated units, glucosamine, could be ionized (pKa ≈ 6.5)
to turn chitosan into a cationic polyelectrolyte, an unusual property for a
biopolymer. Moreover, chitosan amino and hydroxyl groups are suscepti-
ble to chemical modifications that could enhance its functionalities. These
chemical characteristics allow chitosan to set diverse interactions with inor-
ganic and organic compounds. The chitosan features are complemented by
diverse biological properties that include biocompatibility, biodegradability
to harmless products, almost an inexistent toxicity, and specific interactions
with diverse living tissues (bioactivity).

Solubility and Solution Properties

Contrasting with chitin, chitosan can be dissolved in aqueous media [57,58].
Chitosan could be considered a weak base, because the amino groups dis-
tributed along the chitosan molecule could be protonated. It could get a
charge density as high as one cationic charge per glucosamine unit. Thus,
chitosan could go through typical neutralization reactions of alkaline com-
pounds and dissolve in acid aqueous solutions [23,58]. Diluted inorganic
acids, such as hydrochloric, phosphoric, carbonic, nitric and perchloric acids,
are good solvents for chitosan. An exception is the sulfuric acid that gener-
ates the insoluble chitosan sulfate. Chitosan forms soluble salts in numerous
Exploring the Variety of Random
Documents with Different Content
leave the car at the point where the new road mentioned below
diverges at the " Glen " bridge, and after taking the walk along it
and over Glen Head, to rejoin the carriage at Glencolumbkille.
Turning south, opposite the new B.C. Chapel at Ardara, we pursue
the Killybegs road for 1 J miles and then turn to the right up
Glengresh, one of the wildest and most clearly defined valleys
hereabouts, running up between Barkillin (1,291/?.) on the right,
and Glengesh Hill (1,652 /f.) on the left — both nameless on the Ord

 162 SOUTH DONEWAL. nance Survey. The bottom of the
valley is as verdant as a Westmorland dale. Towards the top {abt.
800 ft.) the road gets very steep and zigzags back. A little short of
the watershed a road (quite drivable) turns right and follows the
barren upland valley of the Owenteskiny river for several miles
before making a long descent alongside the Murlin River to the
village of Glencolumbkille, commonly called " Glen." At the expense
of an extra 3 miles or so this route affords a splendid cliff- walk by
which to reach Glencolumbkille. From the near side of the " Glen "
bridge (11 m.) a new road strikes over the ridge, past Longheraherk
and Deamey to the left down a small valley to Port (16 m.). whence
a path leads over the cliff past the Sturral and Glen Head, as
described the reverse way on page 168 to Glencoliimbkille (abt. 5 m.
from Port). The carriage-route, however, continues 1^ miles further
and then turns to the right down the Crow Eiver, which it quits in a
few miles, at the point where the Glen River is crossed. Thence it
proceeds direct to Glencolumbkille. For description of the village, see
p. 168. For Carrick. direct the road follows the Glen River from the
bridge at which the " Glen " road goes off (see map; distance 14 m.
Car-hi7e, abt. Ss.). On nearing Carrick note the profusion of the "
Osmunda." The direct road from Ardara to Klllybegs (9^ m., car-hire,
5s. M.) passes in 4 m. the Nick of the Barr (or Ballagh, abt. 500 ft.),
and then descends by the Stragar River, joining the Donegal and
Killybegs road, 2 miles short of Killybegs close by Ardara Road
Station. This route is to be preferred to the Inver one {p. 161).
SOUTH DONEGAL. Tourists who travel from south to north through
Co. Donegal have the choice between Londonderry, Enniskillen, and
Sligo as starting-places. From Derry they either go without change
from the Midland (Northern Counties Committee) Station on the east
side of the river {see plan, p. 115), or they proceed to Strabane by
the Great Northern, and there change on to the Donegal line — the
stations of the two companies being practically the same. There are
about three through trains a day on the Donegal line, running
through to Donegal and Killybegs, and changing at Stranorlar for the
Glen ties branch. The line is narrow-gauge throughout. From
Enniskellen the route is either by Strabane (45 m.) or by the
Bundoran branch to Ballyshannon (40 m.), and thence by train to
Donegal (14J m.), or still better, by steamer the length of Lough
Erne {p. 181), leaving Enniskillen about 10 a.m., and catching the
afternoon train at Belleek 4 m. short of Ballyshannon. Steamer fares,
2s. and Is. From Sligo the route is by road (mail-car) to Bundoran
(22^ m.) then train to Ballyshannon (26 m.) and Donegal. Two cars
a day.
 LONDONDEEKY TO DONEGAL. 163 Londonderry to
Donegal. Map p. 112. Gt. Northern Route, p. 184. Cyclings, see Pink
Inset. Distances : — Strabane (rail). 15 m. ; Stranorlar, 29 ; Donegal,
47. About three trains a day to Donegal In 2 to 2| hrs. Fares : 6*.
6d., 5js., 3«. lOd. Starting from the Midland Station at Derry the line
skirts the east bank of the Foyle for 3 miles, presenting charming
crossviews of the city. Then it turns in amongst the hills and is no
way remarkable until it re-enters the Foyle valley beyond
Ballyynaporr;/ station, 3 miles short of Strabane. The stream is wide
and the banks for the most part are low and alluvial. Strabane (pron.
Straban. Hotels: Abercorn Arms {Auto., c.t.), Castle Street, bed and
att., 4.s. ; Commercial, about ^ m. from station, where is a
refreshment room on the west side (Donegal platform); Victoria
Temp, (c.t.). Main Street; and restaurant. Pop. 4,200). The three or
four spires of Strabane make the town externally in appearance the
Coventry of Ireland. One of them (10 min. from station) belongs to a
cathedral recently erected. This Cathedral, one of the handsomest
Gothic erections in Ulster, at south end of the to«-n. cost nearly
£15,000. The elaborate spire is nearly 200 ft. high. The chief porch
forms its base. Insule note the pillars of polislierl Aberdeen granite :
the higli and side altars of white Italian marble, and the large E.
window with colours and figures burned in at the making. The
"■stations" are justly admired. The town is an active agricultural
centre, and has a substantial new Town Hall with clock tower, but
has no claim on the tourist, by whom it is, perhaps, best seen from
the railway, in conjunction with its neighbour Zilfford. The latter lies
to the west of the line and enjoys the distinction of being the
"county town" of Donegal, though its population does not reach four
figures. Between Strabane and Lifford the Moiirne coming from the
south, and the Finn from the west— both considerable streams —
join their waters and together assume the name Foyle. Both are
crossed by long bridges, and the churchtower of Lifford is very
picturesque with ivy. Strabane to I/etterkenny, 18 (14 Irish) m. Since
Londonderry was substituted for Strabane as the starting-point for
the Letterkenny mails, this can hardly be called a tourist route, the
scenery along it being commonplace. A new railway has been
constructed by the Midland Company by way of Raphoe, Convoy,
and Glenmaquin, and was opened Jan. 1, 1909. See map, p. 159.
The road crosses the rail a little south of the station, and the Finn by
the old 12-arched bridge just beyond. Then, after passing through
Lifford, it affords a good retrospect over Strabane. The Deele, a
small tributary, is crossed, and soon afterwards, beyond a roadside
inn, from which there is a branch road to Raphoe, we ascend to high
ground and continue along it for several miles. Raplioe lies
considerably to the left of the car-route and is not seen. It is a small
town of about 900 inhabitants, and up to 1835 was the seat of a
bishopric, which was. however, in that year annexed by Derry. The
Cathedral is of no account, and the Bishop's Palace is in ruins. The
name Beltany, a place North Ireland. N
 164 STRANOELAE. 3 miles S. of Kaphoe, reminds us of the
times when the old Druidical "ueed-fires" were lighted on the 1st of
May in honour of the God Bel, as Mr. Robertson, in his " Graelic
Topography of Scotland," tells ns was the custom on Ben Ledi in
Perthshire. On a hill here is an ancient stone circle. Our road, after
continuing over liigh ground for a good distance, descends and
crosses the Letterkeuuy railway at Manor Cunningham Station (111
,^,^_ During the descent fine views present themselves across
Lough Swilly. For the rest of the way we keep more or less near the
railway described on p. 142. For lietterkeniiy, see p. 143. Route
contimted. Crossing the river Mourne we have a good view of the
spires and bridge of Strabane on the left, and on the right of the 12-
arched bridge that sj)ans the Finn at Lifford. Then, striking to the
right on to the Finn Valley branch, we keep the north side of that
river all the way to (14 m. from Strabane). Stranorlar (Hotel: Kee's, J
m. back from station; pop., 420; Eng. let. desp. 2.15, 7.30; Sun. 7.
Del. 7, 11.15, 6.15; Sun. 7). The station is between Stranorlar and
Ballybofey {pron. Ballyho-fay) {M'Gee's and McGlinchey's ; pop. abt.
1000), which are situated in respect of each other similarly to
Strabane and Lifford, being separated by the Finn, which is here
crossed by another bridge of many arches. There are several
mansions in the pleasant neighbourhood— notably Drumhoe Castle
near the river. The most conspicuous building, however, is a new
E.G. Chapel. The Protestant Church is prettily placed in a beech -
grove beyond Kee's Hotel. There is no refreshment-room at the
station. Stranorlar is the better of the two places to put up at.
Cycling from fSti'anorlar. First rate to Strabane, good to Donegal ; 17
Engl. m. Half-way house, with bed. Very fair to Glen ties. To Derry
best by Raphoe. Stranorlar to CJlenties (24^ m.) by rail, narrow
gauge. A convenient route into the heart of Donegal, not to be
recommended, however, to those who have not already travelle
 DONEGAL. 165 and the scarp of Benbulbin to the left of it.
The glen becomes very pretty on the right, and in a few miles we
catch sight of Xioug-ta Eask, with fairly wooded shores and a fine
sweep of mountains — the Blue Stack range — circling behind it. For
ascent, see Mountain Section, p. 214. Loufjh Eask House and other
demesnes are on its shore, and on the island at its south end are the
ruins of (TConnelVs Castle. Clar Bridge station is 2 miles beyond
Lough Eask, and in another 2 miles we reach Map p. 159. Hotels :—
4;-mH .4 rm5(C.T.; bed aa(latt.,3s.); Erin Temp.{C:r.): SttiuUen's;
M'Gintt/s, all in the " Dlamonrl." Pop. 1,400. Mail-car to
Ballyshanuon, 7 a.m.; Sun. 2.20. See description of routes. Post
Office (ill "Diamond") open 7-8; Sun. 8-10. Desp. 12.55 p.m. and 6.5
p.m.; Sun. 4.20. Deliv. abt. 7.20 a.m., 12.45, and 7.30 p.m.; Sun.
8.45. Tel. Office open 8-8 ; Sun. 8-10. Donegal is a prettily placed
but dull little town, with a central square or " Diamond " from which
branch out the different mailroutes. The Abbey and the Castle are
the only things to detain the tourist. Boneg-al Abbey. Take the road
that leads south past the quay. The little nook of Donegal Bay, seen
from here is very pleasing — soft and subdued in character. In 350
yards go over a stone stepstile, or through an iron gate on the right.
The abbey, overlooking the bay, is close at hand. It is a Franciscan
building of the 15th century. Parts of the chancel, with the east
window, the north side of the nave, and the south wall of the
transept remain. On the latter side are the cloisters, with a doorway,
and a number of fine small round arches forming two arcades, 8 on
the east and 6 on the north side. In the churchyard, which is utterly
neglected, is a cross, 12 feet high, to the Rev. J. Doherty (d. 1881).
A return may be made by the waterside. It was in this Abbey that
the "Annals of the Kingdom of Ireland" by the Four Masters was
written. Doneg-al Castle {right of Killyhegs road, key kept by S.
Glen, Quay) shows beautiful remains of the Elizabethan order, and
was the former residence of the O'Donnels. " Tyrconnel," meaning
the "land of Connel," is the Celtic name of Donegal. The ruins
consist of one block, with two bartizan turrets, one of which has
been renewed. The Kitchen, the Wine Cellar, and the Drawingroom
are the chief remaining apartments. In the Drawing-room is a
mantel -piece finely carved with figures and fruit, and the arms of
the O'Donnels and Sir Basil Brooke, who is thought to have rebuilt
the whole.
 166 DONEGAL TO KILLYBEGS. Bonegral to Killybeg-s, 19 m.
(rail) ; and Carrick, 29 m., to Killybegs about 3 trains a day in IJ hrs.
; one Sunday train at 10.5; mail-car (2.^.), 8.40 a.m., Killvbegs to
Carrick (map, p. 159). (a) The Bailwaij, 'I m. longer than the road,
which is hilly throughout, but fair going, rises to Mount Charles ("
Monte Carlo," 4 m.\ Commercial, Temp., c.t. ; Quints Temp., Bay
View) through a well-wooded country passing TJie Hall (Marquis of
Conyngham) and affording a fine view over Donegal Bay of the
boldly scarped mountains of Sligo — the most conspicuous being the
cliff of Benbulbin. Mount Charles is a very strikingly situated village
in full view of the sea. Its population is 250. It has ten licensed
houses, and it is a very healthy place ! From it the line descends to
(8 m.) Znver, at the mouth, as the name implies, of the Eiver Eany,
affording a fine view of the Blue Stack Mountains on the right.
Beyond Inver we cross the base of the long St. John's Promontory,
or rather " Spit," at the end of which is a lighthouse. Then (12 m.)
comes the considerable village of Dunkineely (inns), and soon after,
at 14^ miles (Bruckless) we pass a round belfry tower separated
from the church to which it belongs. A charming view down the
almost landlocked Killybegs Bay follows, and passing (16^ m.)
Ardara-road (for route to Ardara see p. 162) we reach 2J miles
further Killybegs itself. (6) The road rises to 300 feet at Mount
Charles, drops to sea-level at Inver, rises again to abont 200 at
Dunkineely, whence, after another drop to sea-level, it ascends
about 150 feet before finally dropping to Killybegs Harbour. Map p.
159. Distances : — (rail), Donegal, 19 tJi. ; Stranorlar, 37 ; Glenties,
62 ; Strabane 51 ; Derry, 66 ; Enniskillen, 96 : (road), Ardara, 9J ;
Glenties, loj ; Duugloe (by Doochary), 40 ; Gweedore, 53 ; Carrick,
10 ; Glencolumbkille, 16. Hotels: — Coane's, Rogers', C.T., both fair
and reasonable, fani. and comm. A considerable village, gaining
much picturesqueness from the unevenness of its site, and
possessed of several good buildings — the Schools, K.C. Chapel, and
Coastguard Station amongst them. The bay aflEords excellent
anchorage and a pier has been built. The village is also of some
account as a fishery station. In its beautiful harbour the largest
vessels can safely ride at any state of the tide, while at Fintragh, two
miles beyond it, there is a lovely bathing strand. In the gardens of
Fintragh House fruits ripen in the open air such as one only expects
to find in the most favoured nooks of the sunny south. With a little
enterprise there is a fine future for Killj-begs. For Killybeg;s to Ardara
(9^ m.), seep. 162. Xillybegrs to Carrick, 10 m., and
Glencolumbkllle, 16. Map 2?. 159. Mail-car to Carrick (2s.) at 8.15
a.m. From Killybegs
 KILLYBEGS TO CARKICK. 167 the road traverses hillocky
ground for 1^ miles and then descends to Fintragh Bay, on which,
amid the last woods, we may notice Fintragh House. There is a
beautiful sandy beach here, and as we make the long ascent
beyond, the view across Donegal Bay to the shapely inland cliffs on
the south side of it becomes very line. In the mid -distance is the
lighthouse on the long peninsula that ends m St. John's Point, and
S.E. we may detect the long flat top of Cuilgach near Enniskillen and
the source of the Shannon. On our right the mountain- side is dotted
high up with a line of cottages, and in front we look along the coast
to Muckros Head, the western horn of Fintragh Bay, and 8 miles by
road from Killybegs. At this point is a remarkable bit of cliff called "
Muckros Market House." It consists of huge horizontal layers of
limestone and shale as regular as j-ou cut slices off a loaf, the upper
layei-s projecting flat a considerable distance beyond the lower. The
cliffs extend a quarter of a mile, and there are several other caves.
Proceeding, you may reach Kilcar in about 2 miles. Osmunda
abundant. Towards the hill-top, half-way between Killybegs and
Carrick, the road goes inland, and as soon as the highest point is
reached the landward slope of Slieve League comes into full view,
Down in the valley, on the left, at the head of a tiny bay, lies the
village of Kilcar {imb. -houses) a rather slovenly village, through
which the mail-car runs. Then (8^ m. from Killybegs) we may
proceed by either the new road (left, a mile longer) or the old road
(right). In either case the view m descending to Carrick is very
charming, its features being Teelin Bay, Carrigan Head, and Slieve
League. 10 m. Carrick {mail-car to Killybegs (2s.) about 2.35 i):m.
Glencolumbkille Hotel, a capital modern house frequented by tourists
and anglers, who have free fishing — salmon, white and brown trout
— on two rivers and several lakes. B. & A. abt. Ss. 6d. ; Bkft., 2x. M.
; Din., 3^. firf.) is a neat Uttle village, owing its popularity to its
position near the foot of Slieve League and on a favourite route
through Donegal. For Ascent of Slieve Iieagrue, see " Mountain
Section," ^j. 212. It is the home of a remarkable series of rare
alpine plants. Those who wish to see this splendid cliff without
ascending it may either drive (ear 4.s',), or walk to Bunglass Road
along W. side of river for 1| miles ; then second turn beyond stream,
and uphill-road, till you come to a path leading to the beautiful
green-sward of Bung-lass. To the left, on a beetling cliff' is the old
watch-tov,'er on Carrig-an Head, 350 ft. above the sea. In front is a
huge cliff', which is absurdly called pei-pendieular, whereas its strong
point is that it is not perpendicular. No perpendicular cliff' could ever
display such a marvellous contrast of colour — geological and
botanical. Its only rival in this respect in the kingdom is to be found
in the famous Screes over Wastwater in Cumberland, which also
owes as much to vegetable as mineral peculiarities. Oddly enough,
the height of the two only varies by six feet, the height of Slieve
League being
 168 CARRICK TO GLENCOLUMBKILLE. 1,972 feet, and of
the Wastwater Screes 1,978 feet. Wastwater, liowever, is 204 feet
above the sea, so in precipitous descent the Irish cUff has the pull
by all but 200 feet. Some way below the edge of the clili, 96 feet
above our viewpoint, is a spot called the " Eagle's Nest." Tennyson
might have stood on this spot when he wi'ote : — " He clasps the
crag with hooked hauds. Close to the suu in lonely lands, Ring'd with
the azure world, he stands. The wrinkled sea beneath him crawls ;
He watches from liis mountain-walls, And like a tliouderbolt he falls."
Carrick to Glencolumbkille, C m. ; and Ardara, 23. Post-car to
Glencolumhkille and back, Is. (3d. (1 or 2 persons ; 10s. 3 or 4) ;
through to Ardara, I2s. Hd. and 15s. Map p. 159. There are three
ways of continuing the tour northwards from Carrick. (a) The easiest
is by private or public car to Killybegs (10 m., p. 166), and thence by
private car to Ardara (9i m.). This will only be adopted by those who
have made a special visit to Glencolumbkille, and who shrink from
the rough road thence by Glengesh {see p. 161) to Ardara. (b) Up
the Glen river and its tributary the Crow, and from the latter by
Glengesh (14 in. in all, p. 162) ; this for such as have seen
Glencolumbkille and ^vish to reach Ardara by the finest route, (c) By
Glencolumbkille and Glengesh. This last is the only one calling for
description here. The circular drive is best made by Malinmore, and
back direct; whole distance 16 in. The splendid cliffs of Glen Head
are thus presented with an effect as striking as it is sudden. Por a
day's excursion, abt. 18 miles by car and 5 on foot, the drive to Port
by the new road from Grlen Bi-idge, and walk thence over the cliffs
to Glencolumbkille, where the car should be rejoined, is strongly
recommended. See map p. 159, and description on pp. 161, 1G9.
From the hotel the road follows for two miles the course of the small
Owenwee River, which flows from the hollow between Slieve League
and Leahan. At this distance a branch road of five miles strikes off to
the hamlet of Malinmore, which is close to the sea, on the north side
of Malin Bay. Maliubeg:, also close to the sea, is two miles farther
south, opposite the islet of Rathlin O'Birne, on which is a lighthouse,
and under the hill of Leahan (1,413/1.). There is farmhouse
accommodation at Malinmore. Just S.W. of Malin Bay is a horseshoe
bay with a beautiful beach called Trabane ('' white strand "), and the
walk, sometimes tedious, may be continued along the cliff (see p.
212) to the culminating height of Slieve League. In Malin Bay tliere is
also a fine "stack." There are coastguard stations at Malinmore and
on Rathlin O'Bime. Hence we surmount a dreary moorland, and at
about 4 miles commence a steep descent into the valley, in which
lies the scattered and rather abject-looking village of
Glencolumbkille. There is a primitive public-house here. The glen
itself is only a small
 GLENCOLUMBKILLE. 169 one, flanked by low mountains.
Its interest lies in the remains which bear witness to its connection
with the world-famous St. Columb, and the splendid cliff-scenery of
Glen Head. The former are on the road to the latter, a mile north-
west of the village, and near the farthest huts on a little hillock
About in a line with the tower on the Head. The road crosses the
river by a bridge, beyond which, on a mound just on the near side of
the church, is an old and much-worn Cross, said to have been
erected by the saint himself. Then we take a path that crosses the
end of the bay by steppingstones, with a rough causeway beyond,
and ascend to the saint's " Bed,^^ which consists of a few slabs of
stone in an oblong of rough stones, with heaps around it just in
front of the huts. One particular stone is said to have been placed
there by St. Columb, and is now regarded as a talisman against
blindness — the saint having lost the sight of one eye. A little way
beyond and above the Bed is the " Well,'' with a huge pile of stones,
continually increased by the contributions of the "faithful," who have
an implicit belief in the virtues of the mountain-spring, and leave all
manner of testimonials to its healing properties. It lies to the right of
the path, and is easily missed. Beyond this we can ascend for a mile
to the old Martello tower on the summit of Glen Head (745 /t.), one
of the finest cliffs on the Donegal coast, far inferior in height to
Slieve League, but much more abrupt. There is a wide view from the
top, though no great extent of coast is seen, except northwards to
Aran island. The razor edge of Sturrall, just beyond it, is grand. It is
a decided " One-man's Path," and might be thought as easy as
Striding Edge or Slieve League; but Mr, Hart, in his "Climbing in
Ireland," gives an indirect but decided warning. He writes : — '■ "
The knife-edged saddle is very rotten, but leads to a firm block of
rock^ Errigal visible— nearly 1,000 feet above the sea ... . the
passage is not pleasant." The coast to Ardara. A very fine but rough
walk, not much less than 20 miles, and a good day's work. From G-
len Head keep the edge of the cliff, passing Sturrall, which projects j
mile or so. Hence the coast trends eastward, and in a good three
miles breaks into another wild agglomeration of rock called Torinoi*e
Point or Port Hill (815 /'O., before reaching which, however (2 ;«.
beyond Sturrall), we pass a narrow cleft with vertical sides and
descending almost to sea-level. It is called the Saicpit, or " Port." For
new road hence see p. 162. Between it and the Port promontory is a
.soi-dmint little harbour— the original of the name Port — and a
bothy or -two, whence we ascend to the promontory and from the
cliff top look down the broken and distorted line of crag that ends in
Tormo/e Island — Mortehoe on treble the scale. The island is a great
Iji-eeding-place of sea-birds, and is accessible from the mainland at
low-tide. The cliff' now circles down to sea-level, at a spot called
Pitliska, where, at the foot of the Glenlough streamlet, there is a
quiet little bay. Thence Slieve Tooey blocks the way, the cliffs again
rising to a great height. We have no personal experience of the
route over it to Maghera. It is probably the best plan to go inland,
and along the ridge of the mountain, descending by the Owenwee
River to the hamlet of Maghera, a rough 9 or 10 miles from Port.
Along the cliff-route there appears to be a precipitous descent from
a height of 331ft. opposite Gull Island to the streamlet main from
Lough Adoochree, whence Ardara is reached by road in 5-6 miles
{pp. 159, 160).
 170 DONEGAL TO BALLYSHANNON. Doneg-al to Ardara,
18^ m.; mail-car (2s. 6d.), abt. 8.30 {Sundays only). Map 2?. 159.
As far as Inter (7 m.) the route is the same as to Killybegs (p. 166),
and the rest of it is sufficiently described the reverse way on JO.
161. For zlrdara, see^). 159. Donegal to Ballyshannon, ^H m-;
Bundoran, 18^; and Sligo, 41. Map;?. 176. Mail-cars :— Donegal to
Ballysbannou (2 hrs., 28.), abt. 7 a.m. (Su)i. 8.30); returning abt,
4.10 p.m. ; Ballyshannon to Sligo (4 hrs., 3s. M.) abt. 7 a.m. and 3
p.m. {Sun. 2.30.) There is a rail connection to Bundoran by 12.25
and 7.5 (Donegal Railway) changing at Ballyshannon to G.N. line
with one half to one hour to wait. For Bundoran they may proceed
from Ballyshannon by train about 10, 2.16, and 8.10, or they may
hire at any time (4 7«.). The "lions" of Ball3-shannon— the "rapids"
and the "salmon leap"— may both be seen from the bridge between
the hotels and the railway station. The route is fairly interesting as
far as Ballyshannon, beyond which it runs for about 15 miles near
the sea, affording a fine view across Donegal Bay ; then it turns
inland along the foot of the clitf-like limestone ridge of which
Benbulbin (1,712 ft.) is the most striking though not the highest
summit. Quitting Donegal we pass Donegal Abbey {p. 165) and, half
a mile further, the fragments of Magherabeg Abbey. The country
hereabouts is well wooded and pastoral. From l.ag:liy (3^ m., lie.
ho.) a road 13 miles long goes over a bleak and dull country to
Pettigo (p. 185). At Ballintra (7 J m., pub. ho., note the walnut-tree)
we enter the limestone district. At Brownhall, 1^ miles to our left,
the Ballintra Eiver plunges do^vn a deep wooded gorge called "The
Pullins," pursuing a course alternately above and under ground after
the characteristic manner of streams in limestone districts, finally
coming out on to the level through a natural arch a little short of
Ballintra. The Piper's and the Sheepskin Caves contain stalactites
and stalagmites. Rossnowlagh (station) is a rising wateringplace with
a three-mile firm strand. There is nothing else of special note till we
reach (14^ m.) —
 BALLYSHANNAN. 171 Mouth of Shannagh's Ford." aotelm:—
Imperial, Royal Temp. (Auto, and Mot; U., C.T.), G?-aham's Temp.,
Assroe Temp., all north of river. Post Office :— Open 7-8. Del. 8.20,
10.40, 2.40, 4.55 ; Sun. 8.30. Des. 11.20, 4.50 ; Siai. 4.1U. Tel. Off.
8-8. Railway Stations: — G.N. over bridge on south side of river.
Donegal, on north side of river. Rail to Enniskilleu and Buudorau ;
mail-cars to Siigo (^seep. 172) and Donegal about 4 p.m., Sun.
2.20. Pop. 2,750. The town rises from both banks of the Erne at the
head of its estuary. An old buttressed bridge of 12 arches spans the
stream, and from it the visitor may see the two features of the
locality — the rapids, | mile up-stream, and the salmon leap, ^ mile
below. A little above the bridge an eel-weir is thrown across the
river. The slope on which the northern (chief) part of the town rises
gives it from a distance an attractive appearance, which, however,
hardly bears the test of closer investigation. The south side is very
mean and untidy. The G.N. station is, on that side, 8 minutes' walk
from the bridge, on which is a tablet recording the town as the
birthplace of the poet, W. Allingham. For the Rapids take the road
that goes east from the Market Hall, parallel to the river, and in |
mile, after passing, on the right, the Convent, cross a stone step-
stile into the fields. The stream is for 100 yards, more or less,
confined by Limestone rocks to a narrow channel down which it
pours its troubled waters with headlong speeJ and, after much rain,
an almost deafening roar. For the Salmon l.eap go west along the
narrow street, in which is the Post Office, for ^ mile and, passing
the graceful Presbj-terian Church, cross a stile opposite the National
School. The fresh water leaps into the tidal estuary over a barrier of
rock that forms an obtuse angle in the direction of the stream in the
middle. At low -tide the height is about 20 feet, but at spring-tides
the sea-water rises to within a few feet of the top. The cataract is a
very fine one, and in the spring months, when the salmon are
coming up from the sea, the scene is exciting. Funnel-shaped traps
are laid in different parts, into which the unwary fish now and again
leap. The river is divided into seven beats, and there are four miles
of fishable water— between Ballyshannou and Belleek. The charge
for salmon-fishing is £4 a week ; trout, £1. Of Assaroe Abbey (1 mile
N.W. of the town ), a Cistercian foundation of the 12th century, a
few fragments remain. There are many Danish Raths near
Bally)ianuou. (Rail to Enniskilleu, see p. 184.) Ballysbannon to
Bundoran (4 m.) and Sligo (26 ni.). Cars aht. 7 a.m. and S p.m. Fare
3s. 6d. ; continuation of route on p. 174 {aht. 4t trains a day to
Bundoran). M&y p. 172. The road traverses an almost level tract of
country that lies between Donegal Bay and a range of bold and lofty
limestone cliffs till, approaching Sligo. it recedes a little from the
shore, and enters a more undulating region.
 172 BUNDORAN. Postal Address: — "Bundorau, Ireland.'
Map opposite. Tourist Tickets from Dublin :— 35a\ 6d., 27s. 6d., 18s.
; from Belfast, 27s. 6(/., 22s., I5s. for one passenger ; less in
proportion for two, three, or four. Express from Dublin (Amiens
Street) about 9 a.m., Belfast, 9.30, in 4|-5 hours, see Great Surtheni
Tou/ist Programme ; also for combined rail and hotel tickets {seep.
48). Hotels : — Great Northern (first-class ; commanding situation,
on golf-ground, overlooking the sea, ^ mile from station, closed
from Oct. 20th to April 6th) : full terms, 63s. a week ; bed and att.
from 3s. 6(7. ; lunch, 2s. M. ; bkft.. Is. %d. to 2s. 6cZ. ; table-d'hote
din., 4s. Central, late Sweeny's, bed and att. from 2s. &d. ; din., 3s.
Meetuin's, O'Gorman's, east end ; Royal, west end ; Atlantic, east
end, smaller, and The Lodge, C.T. (Board. Hse., R&ivy) ; Hamilton's,
from 5.5s. a week ; Maj-ine, about 45s. a week. Ijarge Tea Riu. to
right above station at popular prices. Rail to Ballyshannou (4 m.),
Enniskilleu (44 m.), about 4 trains a day in l|-2 hrs. Fares : about
2*/., IJt/., and Id. a mile. Coaching Excursions (July and Aug.) from
Great Northern Hotel, 3 or 4 days a week to Donegal, by the Pullius
(3s. 6d.) ; round Loch Melvin by Grarrison and Belleek, MuUaghmore
by coast, etc. Distances : — (By rail), Ballyshannon, 4 m. ;
Enniskillen, 44 : Londonderry, 87 ; Belfast (by Enniskillen), 130 ;
Greenore (by Enniskillen and Duudalk), 120 ; Dublin, 160. Through
passengers by night boats from England leave Dublin about 9 a.m.,
Greenore 9.40, and Belfast (from Scotland also) about 9.30,
reaching Bundoran about 2.25. Mail-cars :— To Sliyo (3s.), abt. 7.45
a.m. and 3.35 p.m. Post Oltice, 2 Bav View Terrace .—Open 7-8 ;
Sun. 8-10.30. Chief desp. about 11.5, 4 ; Sun. 3.30, 5 ; del. 9.45, 3.
Tel. Off. open 8-8 ; Sun. 8-10. Bundoran is the favourite — perhaps
the only — watering-place in this part of Ireland. It consists of one
irregular street, parallel with and a little way off the shore, in length
nearly a mile. The " fashionable " part is the western half. The
situation is somewhat bare and unprotected, but in full command of
a fine open sea, with the Donegal Mountains, ending in Slieve
League, on the far side, 12 to 20 miles away. Inland the tameness of
the foreground is relieved by the singular cliff-like mountains we
have already mentioned. Along the shore are sandy nooks, well
adapted for bathing, and the low limestone cliff is a good deal
contorted. There is a path along the cliffs in both directions : —
Eastward round the golf-course to (1 m.) the Fairy Bridge, and then
down to a splendid bay of yellow sand ; westward for nearly two
miles over the low cliff, consisting mostly of horizontal sandstone
slabs to the mouth of the Drowes Eiver, which flows out of Lough
Melvin. In both directions the walk is in fine weather of a breezy and
delightful character, and the views across Donegal Bay to Slieve
League and the heights extending thence to the Blue Stack
Mountains; while to the south-west the strangely sculptured Dartry
Heights— or rather cliffs— Benbulbin and others— of the
The text on this page is estimated to be only 9.57%
accurate

^.???| SLIGO, BUNDORAN & BALLYSHANNON Irujlak Mia

 THE FAIRY BRIDGE. 173 individual names of which the
Ordnance Survey has been extremely neglectful, are very striking.
The weakness of Bundoran is dulness and bareness of foreground
landwards, and treelessness. In this last respect it is even worse
than Llandudno. So far, too, the town is somewhat of a laggard in
the amenities of an up-to-date watering-place. There is no gas, and
up to within a late period it had no chemist or barber. The general
appearance of the place is somewhat mean and the shops are poor.
Apparently no provision is made for wet days. The splendid golf -
ground, however, and the erection of the new hotel (electric lighted)
have given the place a tremendous fillip. The climate (much
recomraemled by the late Sir Morell Mackenzie) is excellent, bracing,
and at the same time free from extremes of heat and cold. Though
the town is 200 miles further north than London, the isothermal line
on which London stands passes as much as 80 miles north-west of
Bundoran. Needless to say the Gulf Stream is accountable for tliis
peculiaritj". The average yearly rainfall is a little over iO inches.
Bundoran looks its liveliest on a fine Sunday in the season. Two
heavj- excursion trains, starting from Derry and Clones respectively,
bring their scores of holiday-makers on that daj'. The Batliing; is
excellent, though somewhat primitive. Still many will prefer the
freedom of a semi-alfresco loose box comfortably carpeted with hay,
the use of which may be obtained at Id. or 2(1. a head, and a
bucket of fresh water as a footpan, to the dank discomfort of an
orthodox English bathing-machine at 6(/. Ladies are somewhat more
scrupulously provided for. "With a good westerly or nor'-westerly
breeze a fine sea comes rolling in. On occasions the rocky horizontal
slabs that foi-m the shore west of the town are very tempting for a
dip, the chief resorts being Priest's Pool and Roguey. There are also
some baths in a meadow by the church. The Palry Bridg-e is reached
in about 1^ miles' walk by a lane at the side of the Central Hotel and
across the sands and up some steps and by a fenced-olf path along
the cliff and round the goli-ground. It is a tine natural arch formed
by the irruption of the sea, which has also caused a good deal of
laud or rather rockslip about here. Beyond it is the fine stretch of the
Tiillan Strand, which extends to the narrow mouth of the Erne, IJ
miles distant. Westu'ard from the town there is a path near the cliff-
edge as far as the mouth of the river Droicse (2 m.). Towards the
end of it a tower is passed which contains rough and broken pieces
of sculpture, the eccentric work of a Mr. Cassidy, formerly owner of
the Bundrowes salmon-fishery. We now rejoin the road and cross the
Drowes, "noticing the fishery works. A few yards further is a small
licensed-shop on the right and' there is another at Tullag-han, half a
mile further, just beyond which, on the left of the road, is an old
cross 10 feet high, removed to this spot in 1778 from the seashore
and erected by Thomas Dickson. Close by, up a by-road, the scanty
ruin of Duncartry Castle crowns a mound from which there is a fine
view of the Dartry Mountains and across Donegal Bay ; and close by
is Duncartry Cottage, thatched, gabled, and reminding one
somewhat of the cottage — Plas Newydd — of the two famous Irish
ladies of Llangollen at the town of that name.
 174 LOUGH MELVIN. Xioug-li Melvln, 2 miles distant by the
road that strikes S. from the middle of the town, is a fine sheet of
water 8 miles long by from 1 to IJ wide. About eight islets, mostly
well- wooded, stud its surface. The most central one, hiish Temple,
is so called from an old church on its southern shore, a mile E. of
which, close together, near the northern shore, are Inishkeen
("beautiful island ") and Rossnit. A tiny islet 1^ miles from the W.
end of the lough, and within a stone's throw of the S. shore supports
the ruin of Rossclogher Castle with an old church or "abbey" on the
mainland opposite. The castle was a stronghold of the M' Clancys,
chiefs of the Dartry district. The drive round is 23J miles. The north
shore of the lough is tame, but on the S. side the hills rise to a
considerable height (1,700 /^), and the scenery is very picturesque.
At their feet are the residences, Kinlough House and Mount
Prospect. The lough affords excellent salmon and trout fishing-. {See
Fishing Section.) Besides the hotels at Bundoran and Belleek (4J )n.
from the E. end of the lough, p. 185) there is a small angler's inn at
G-arrison [Scott^s ; 12 visitors; 42s. a week), a village at the E.
extremity, so called from its having been a military station in the
rebellion of 1641, and a licensed house at Kinlough, the nearest
point to Bundoran, besides other lodgings. from just beyond ilt.
Prospect, 3 ??k from Kinlough, a road strikes oS. to the head of Glen
Aiiiff, after descending the full length of which it eaters in about 6
miles the Belleek and ilanor Hamilton Eoad, 6 miles short of the
latter town. Bundoran to iSlig^o (direct pedestrian route), rid G-
lencar Waterfalls; about 22 m. This is a very fine walk which can,
however, be shortened by taking a car for the first 8 miles or so. A
mail-car leaves Bundoran about 9.15 a.m. for (llenade, 8^m. Leave
Bundoran by the Manor Hamilton road ( W. side of bridge) and drive
or walk to within 1 or 1^ m. of the head of trlenade Lough (8 m.).
passing (3 m.) the village of Kinlough ("Head" of '-Lough" Melvin ;
pub.-ho.). Thereabouts a road diverges on the right, crosses the
valley, and seems to lead nowhere in particular. Go down this road
and on the side of the mountain opposite you will see— apparently
the only way up the cliffs — a sort of path ascending from left to
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