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Renewable resources for biorefineries

Carol Lin
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Renewable Resources for Biorefineries


View Online

RSC Green Chemistry

Editor-in-Chief:
Professor James Clark, Department of Chemistry, University of York, UK
Published on 11 August 2014 on http://pubs.rsc.org | doi:10.1039/9781782620181-FP001

Series Editors:
Professor George A Kraus, Department of Chemistry, Iowa State University,
Ames, Iowa, USA
Professor dr. ir. Andrzej Stankiewicz, Delft University of Technology,
The Netherlands
Professor Peter Siedl, Federal University of Rio de Janeiro, Brazil
Professor Yuan Kou, Peking University, China

Titles in the Series:


1: The Future of Glycerol: New Uses of a Versatile Raw Material
2: Alternative Solvents for Green Chemistry
3: Eco-Friendly Synthesis of Fine Chemicals
4: Sustainable Solutions for Modern Economies
5: Chemical Reactions and Processes under Flow Conditions
6: Radical Reactions in Aqueous Media
11:50:18.

7: Aqueous Microwave Chemistry


8: The Future of Glycerol: 2nd Edition
9: Transportation Biofuels: Novel Pathways for the Production of Ethanol,
Biogas and Biodiesel
10: Alternatives to Conventional Food Processing
11: Green Trends in Insect Control
12: A Handbook of Applied Biopolymer Technology: Synthesis, Degradation
and Applications
13: Challenges in Green Analytical Chemistry
14: Advanced Oil Crop Biorefineries
15: Enantioselective Homogeneous Supported Catalysis
16: Natural Polymers Volume 1: Composites
17: Natural Polymers Volume 2: Nanocomposites
18: Integrated Forest Biorefineries
19: Sustainable Preparation of Metal Nanoparticles: Methods and
Applications
20: Alternative Solvents for Green Chemistry: 2nd Edition
21: Natural Product Extraction: Principles and Applications
22: Element Recovery and Sustainability
23: Green Materials for Sustainable Water Remediation and Treatment
24: The Economic Utilisation of Food Co-Products
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25: Biomass for Sustainable Applications: Pollution Remediation and Energy


26: From C-H to C-C Bonds: Cross-Dehydrogenative-Coupling
27: Renewable Resources for Biorefineries
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Renewable Resources for


Biorefineries
Published on 11 August 2014 on http://pubs.rsc.org | doi:10.1039/9781782620181-FP001

Edited by

Carol Sze Ki Lin


City University of Hong Kong, Hong Kong
Email: carollin@cityu.edu.hk

Rafael Luque
University of Cordoba, Spain
Email: q62alsor@uco.es
11:50:18.
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RSC Green Chemistry No. 27

Print ISBN: 978-1-84973-898-9


PDF eISBN: 978-1-78262-018-1
ISSN: 1757-7039
11:50:18.

A catalogue record for this book is available from the British Library

r The Royal Society of Chemistry 2014

All rights reserved

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Published on 11 August 2014 on http://pubs.rsc.org | doi:10.1039/9781782620181-FP007

Preface

With an increasing awareness and concerns about our dependency on fossil


resources and the depletion of crude oil reserves, this book aims to give an
overview to the bio-based economy. Experts from academia and industries
worldwide have presented their views on industrial biotechnology, green
chemistry and sustainable policy related to the use of renewable raw ma-
terials for non-food applications and energy supply. Innovative key research
concepts such as waste valorization and its society aspects related to
renewable resources need to be transferred to the public, academic and
industrial sectors in order to redouble efforts towards a more sustainable
society and a bio-based economy.
11:50:19.

This book is a concise presentation of a variety of such important aspects


in renewable resources and biorefineries. Key features of the book include
guidelines for appropriate practices on biorefineries and understanding
of waste valorization and bio-processing, with updated latest information
on international research and development of novel green strategies and
technologies for utilization of renewable resources. The book contains eight
high quality chapters, detailing both theoretical and practical information
with the aim to provide inspiration for additional research and application
to generate energy and value-added products. Bio-based polymers and
materials, downstream processing of bioplastic materials, enhanced biomass
degradation by polysaccharide monooxygenases, microalgae technology,
application of food waste valorization technology in Hong Kong, advanced
generation of bioenergy, pre-treatment and transformation of ligno-
cellulosics, and bioactive compounds from biomass are topics extensively
covered in this monograph.
As editors of this book, we sincerely hope it can serve as a starting point to
highlight the importance of industrial biotechnology and green chemical
processes and technologies in biorefineries for the benefit of humankind.

RSC Green Chemistry No. 27


Renewable Resources for Biorefineries
Edited by Carol Sze Ki Lin and Rafael Luque
r The Royal Society of Chemistry 2014
Published by the Royal Society of Chemistry, www.rsc.org

vii
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viii Preface

We would also like to take this opportunity to acknowledge and thank all
the contributors to this book for their excellent collaboration and timely
contributions which brought together a highly comprehensive range of
topics. Many thanks to Merlin Fox, Commissioning Editor for the Green
Chemistry Series at Royal Society of Chemistry (RSC) and the production
Published on 11 August 2014 on http://pubs.rsc.org | doi:10.1039/9781782620181-FP007

team at RSC, particularly Helen Prasad, for her helpful assistance through
this project and ensuring everything came together properly.
With very best wishes for successful and enjoyable reading.

Carol Sze Ki Lin


Rafael Luque
11:50:19.
Published on 11 August 2014 on http://pubs.rsc.org | doi:10.1039/9781782620181-FP009

Contents

Chapter 1 Bio-based Polymers and Materials 1


Nathalie Berezina and Silvia Maria Martelli

1.1 Introduction 1
1.2 Direct Production of Biopolymers 2
1.2.1 PHA 2
1.2.2 Polysaccharides and Oligosaccharides 5
1.2.3 Others 9
1.3 Production of Bio-based Monomers for Further
Polymerization 13
1.3.1 Lactic Acid and PLA 13
1.3.2 1,3-Propanediol and Soronas 14
11:50:20.

1.3.3 Succinic Acid and PBS 16


1.3.4 Others 16
1.4 Outlook 20
References 21

Chapter 2 Fundamentals and Biotechnological Applications of


Downstream Processing Technologies 29
Raquel Manozzo Galante, Gustavo Graciano Fonseca,
Nathalie Berezina, Thiago Caon, Farayde Matta Fakhouri
and Silvia Maria Martelli

2.1 Introduction 29
2.2 Downstream Processing Steps 31
2.2.1 Cell Inactivation 34
2.2.2 Clarification 35
2.2.3 Liquid/Liquid Extraction 40
2.2.4 Cell Disruption 43

RSC Green Chemistry No. 27


Renewable Resources for Biorefineries
Edited by Carol Sze Ki Lin and Rafael Luque
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ix
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x Contents
2.2.5Polishing 46
2.2.6Non-chromatographic Approaches for
Purification 49
2.3 Examples of Downstream Processing of Different
Products 51
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2.3.1 Recovery of Biopolymers or Bio-based


Monomers for Further Polymerization 51
2.3.2 Pharmaceutical Applications: Viral Vectors,
Plasmid and Vaccine Manufacturing Processes 53
2.4 Conclusions 57
References 57

Chapter 3 Enhanced Biomass Degradation by Polysaccharide


Monooxygenases 64
Tanghe Magali, Danneels Barbara, Stals Ingeborg and
Desmet Tom

3.1 Introduction 64
3.2 Synergy in Cellulose Degradation 65
3.3 Protein Structure 67
3.3.1 Overall Fold 67
3.3.2 Conservation 68
3.4 The Oxidative Reaction 69
11:50:20.

3.4.1 Reaction Components 69


3.4.2 Location of Oxidation 70
3.4.3 Putative Reaction Mechanism 70
3.4.4 Similar Reactions 71
3.5 Activity Measurement 73
3.5.1 Colorimetric Methods 73
3.5.2 Analytical Methods 74
3.6 Classification 75
3.7 Conclusion 76
Acknowledgements 77
References 77

Chapter 4 Microalgae Technology 79


Zheng Sun, Yan-hui Bi and Zhi-Gang Zhou

4.1 Introduction 79
4.2 Mass Cultivation 80
4.2.1 Open Pond System 80
4.2.2 Photo Bio-reactor (PBR) System 80
4.3 Cultivation Mode 81
4.4 Biomass Processing 83
4.4.1 Harvesting 83
4.4.2 Dewatering 84
View Online

Contents xi
4.4.3 Extraction 84
4.4.4 Oil Transesterification 85
4.5 Improving the Economics of Microalgal Oil 86
4.5.1 Genetic Engineering 86
4.5.2 Biorefinery-based Production Strategy 87
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4.5.3 Development of Low-cost Carbon Source 89


4.6 Conclusions and Outlook 90
Acknowledgement 90
References 90

Chapter 5 Application of Food Waste Valorization Technology in


Hong Kong 93
Kwan Tsz Him, Carol Sze Ki Lin and Chan King Ming

5.1 Introduction 93
5.1.1 Characteristics of Food Waste 93
5.1.2 Definitions of Food Waste 94
5.1.3 Limitations of the Application of Food Waste
Valorization Technology 94
5.2 Current Status of Food Waste in Hong Kong 95
5.3 Overview of Food Waste Valorization Technology 99
5.3.1 Waste to Soil: Composting 99
5.3.2 Waste to Food Chain: Animal Feed Production 100
11:50:20.

5.3.3 Waste to Energy: Incineration 102


5.3.4 Waste to Energy: Anaerobic Digestion 103
5.3.5 Waste to Biomass Resource 104
5.4 Advantages and Disadvantages of Food Waste
Valorization Technologies 105
5.4.1 Waste to Soil: Composting 105
5.4.2 Waste to Food Chain: Animal Feed
Production 106
5.4.3 Waste to Energy by Incineration 107
5.4.4 Waste to Energy by Anaerobic Digestion 107
5.4.5 Waste to Biomass Resource 108
5.5 Food Waste Valorization Technologies
in Hong Kong 108
5.5.1 Composting 109
5.5.2 Animal Feed Production 109
5.5.3 Incineration 109
5.5.4 Anaerobic Digestion 111
5.6 Suitable Technologies for Hong Kong 111
5.6.1 Commercial and Industrial Food Waste 111
5.6.2 Domestic Food Waste 111
5.7 Conclusions 113
Acknowledgements 113
References 113
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xii Contents
Chapter 6 Advanced Generation of Bioenergy 117
Oluwakemi A. T. Mafe, Nattha Pensupa, Emily May Roberts
and Chenyu Du

6.1 Biofuel Introduction 117


Published on 11 August 2014 on http://pubs.rsc.org | doi:10.1039/9781782620181-FP009

6.2 First Generation Bioethanol Production 118


6.2.1 Milling 118
6.2.2 Liquefaction and Saccharification 119
6.2.3 Fermentation 119
6.2.4 Distillation 120
6.2.5 Dehydration 120
6.3 Introduction of Advanced Generation Bioethanol
Production 120
6.3.1 Advanced Generation Bioethanol Production
Process 121
6.4 Lignocellulosic Feedstock 121
6.4.1 Cellulose 123
6.4.2 Hemicellulose 123
6.4.3 Lignin 123
6.5 Pre-treatment 123
6.5.1 Physical Pre-treatment 124
6.5.2 Chemical and Thermochemical
Pre-treatment 125
11:50:20.

6.5.3 Biological Pre-treatment 128


6.6 Detoxification 130
6.7 Hydrolysis 130
6.7.1 Glycosyl Hydrolases 130
6.7.2 Enzyme Production 132
6.8 Fermentation 132
6.8.1 Yeast Fermentation and Yeast Genetic
Modification 132
6.8.2 Yeast and Tolerance to Inhibitors 134
6.8.3 Co-fermentation using Yeast Strains 137
6.8.4 Thermophilic Bioethanol Production 139
6.9 Conclusion 140
References 141

Chapter 7 High Value Chemicals and Materials Production Based on


Biomass Components Separation 146
Jie Chang

7.1 Introduction 146


7.2 Separating the Components of Biomass 147
7.2.1 Acid Hydrolysis for Biomass Separation 148
7.2.2 Alkaline Hydrolysis for Biomass Separation 148
View Online

Contents xiii
7.2.3Ammonia Fiber Expansion for Biomass
Separation 148
7.2.4 Hydrothermal Treatment for Biomass
Separation 148
7.2.5 Organic Solvent for Biomass Separation 149
Published on 11 August 2014 on http://pubs.rsc.org | doi:10.1039/9781782620181-FP009

7.2.6 Ionic Liquid for Biomass Separation 149


7.2.7 Biomass Separation and Production of
Chemicals and Fuels 153
7.2.8 Summary 153
7.3 Chemicals Production From Lignin 154
7.3.1 Lignin-based Materials 154
7.3.2 Lignin Application in Carbon Fibers 154
7.3.3 Polymer Modifiers 155
7.3.4 Resin, Adhesives, Binders and Others 157
7.3.5 Power, Fuels and Syngas Products 157
7.3.6 Liquefaction to Prepare Value Added
Phenolic Compounds 159
7.3.7 Summary 160
7.4 Upgrading of Cellulose and its Products 160
7.4.1 Structures and Properties of Cellulose 160
7.4.2 The Catalytic Conversion of Cellulose to
Fuels and Chemicals 161
7.4.3 Functional Cellulose Materials Prepared
11:50:20.

from Non-derivatizing Solvents 162


7.4.4 Derivative Modification of Cellulose and
Graft Copolymers 164
7.4.5 Summary 164
7.5 Chemicals and Materials from Hemicellulose 165
7.5.1 Fractionation and Purification of
Hemicelluloses 165
7.5.2 Enzymatic Hydrolysis of Hemicelluloses 166
7.5.3 Materials and Chemicals from Hemicellulose 166
7.5.4 Applications 170
7.5.5 Summary 170
7.6 Conclusions and Suggestions 172
Acknowledgements 173
References 173

Chapter 8 Bioactive Compounds from Biomass 176


Chun-Ping Xu and Rick Arneil D. Arancon

8.1 Value of Biomass 176


8.1.1 Introduction 176
8.1.2 Screening of Bioactive Activity from Biomass 177
8.2 Bioactive Compounds from Biomass 178
8.2.1 Carbohydrates 178
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xiv Contents
8.2.2 Peptides and Proteins 179
8.2.3 Secondary Metabolites 179
8.3 Case Study: Bioactive Compound from
Tobacco Waste 181
8.3.1 Sclareol 182
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8.3.2 Alkaloids 182


8.3.3 Solanesol 183
8.3.4 Proteins and Amino Acids 183
8.3.5 Organic Acids 184
8.3.6 Carbohydrates 184
References 184

Subject Index 187


11:50:20.
Published on 11 August 2014 on http://pubs.rsc.org | doi:10.1039/9781782620181-00001

CHAPTER 1

Bio-based Polymers and


Materials
NATHALIE BEREZINA*a AND SILVIA MARIA MARTELLIb
a
Materia Nova, Rue des Foudriers 1, 7822 Ghislenghien, Belgium;
b
Faculty of Engineering, Federal University of Grande Dourados,
Dourados, Brazil
*Email: nathalie.berezina@materianova.be

1.1 Introduction
11:50:21.

Biomaterials have gained attractiveness in the last decades due to both


ecological and economic concerns. Increased pollution, and especially
visible pollution, has first driven the scientific and industrial communities
to look at biofragmentable and biodegradable substitutes for traditional
petroleum-based non-biodegradable materials. Then the dramatic increase
of oil prices before the economic crisis of 2007 influenced the move from the
biodegradable to the bio-based. Finally, the compliance of the obtained
materials with thermo-mechanical constraints has turned interest to the
partially bio-based materials.
Bio-based materials can be obtained mainly by two different ways: the
direct production of polymers or the production of bio-based monomers and
their further (bio)chemical polymerization. The direct production of bio-
polymers can be achieved by microorganisms (polyhydroxyalkanoates, PHA),
by algae (alginate etc.), by superior plants (pectin etc.) or by several types of
producers, e.g. cellulose is produced by superior plants but also by bacteria,
chitosan is produced by crustacean but also by fungi.

RSC Green Chemistry No. 27


Renewable Resources for Biorefineries
Edited by Carol Sze Ki Lin and Rafael Luque
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1
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2 Chapter 1

Whatever the producer of biopolymers, the main difficulty is to trigger its


composition. Indeed, the obtained material has to comply with the thermo-
mechanical constraints of its anticipated usages, and these characteristics
are strongly related to the monomeric composition of the polymer and its
size. This common problem of biopolymers does not have a unique solution.
Published on 11 August 2014 on http://pubs.rsc.org | doi:10.1039/9781782620181-00001

In the case of PHA, several microorganisms can produce the same polymer
and the modification of the feeding substrates influences the monomeric
composition of the polymers produced by the same microorganism, whereas
important differences are found in the monomeric composition of the poly/
oligo-saccharides produced by different (micro)organisms. The regulation of
the size of the biopolymers appears even more complicated; although PHA
can be obtained with important masses, polysaccharides are actually mainly
oligosaccharides. In any case, the main difficulty consists in making the
(micro)organism perform the biosynthesis we want consistently and
repeatedly.
To circumvent this problem, one can be tempted to make more controlled
chemical polymerization with the bio-based monomers. Thus the pro-
duction of bio-based monomers was also developed. However, the poly-
merization of bio-based monomers often asks for more development, as in
the case of polylactic acid (PLA) and of polybutylene succinate (PBS);
moreover, the thermo-mechanical needs for the expected applications are
hardly reached with these polymers. Therefore, two more options can be
foreseen: the production of partially bio-based materials (Soronas) or the
11:50:21.

production of bio-monomers identical to the already existing and improved


petroleum-based (ethylene, isobutylene, caprolactam etc.).
In this chapter we discuss the main biomaterials produced by these dif-
ferent methods as well as the achieved improvements and remaining
bottlenecks in their production, modifications and applications.

1.2 Direct Production of Biopolymers


1.2.1 PHA
Polyhydroxyalkanoates (PHA) were discovered in 1926 by Maurice Lemoigne1
as energy storage materials in Bacillus megatherium and Bacillus mesentericus
vulgatis. Still, they had to wait until the 1960s and for Cupriavidus genera
(previously referred as Hydrogenomonas, Alcaligenes, Ralstonia and Wautersia)
to be extensively studied.2–4 Indeed, the accumulation of the PHA by this
genera has appeared to be more effective. Moreover, the first petrol crisis
and further ecological issues increased the awareness and the interest in the
bio-based materials.
Several PHA producing microorganisms as well as several types of PHA
were discovered.5–8 The whole PHA family can be sub-divided into three
main categories: the short-chain length PHA (PHASCL), the medium-chain
length PHA (PHAMCL) and rarer PHA (Figure 1.1). The structural differences
inside the PHA family imply deep differences in their thermo-mechanical
View Online

Bio-based Polymers and Materials 3

O O
p
PHASCL-co-PHASCL
O O
m
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n
R O

O O
O
n P3HA-co-P4HA
O O
n m

R - alkyl group
PHASCL - R bearing less than 3 carbons O O
PHAMCL - R bearing 3 or more carbons P3HA-co-P3MP
O S

n m

Figure 1.1 Major types of PHA found in the nature.

properties. Thus, PHASCL mainly composed by polyhydroxybutanoates (PHB)


and poly(hydroxybutanoate-co-valerate) (PHBV), are crystalline polymers,
which are rather brittle and stiff, with high melting points (near 160–180 1C)
and low glass transition temperature (between 5 and 0 1C), whereas the
PHAMCL are thermoplastic elastomers with low crystallinity and tensile
11:50:21.

strength with high elongation to break (400–700%).9,10

1.2.1.1 PHASCL
PHASCL are the most studied biopolymers among the PHA family. Numerous
improvements of their production have been achieved during these last
decades. These improvements mainly concerned the selection of wild-type
strains (121 g L 1 of PHB was thus achieved using Cupriavidus genera11), the
engineering of strains (161 g L 1 of PHB was reported with E. coli (XL1-Blue)
strain11), the feeding strategy ‘nutrient limited’ versus ‘nutrient sufficient’
conditions,12,13 with the latter having been recently proved to be most effi-
cient for the main producing strains (33 times productivity enhancement14).
Also, the growth and the PHA accumulation on wastes and by-products
have been paid important attention in recent years, in order to enhance the
economic and sustainable efficiencies. Thus, different alternative substrates
were tested – such as vinasse,15 oil palm frond juice,16 soybean oil,17 waste
glycerol18 and other by-products from the biodiesel industry.19,20 Unfortu-
nately up to now these strategies have not shown comparable productivities
as an artificial carbon source (only 67.2 g L 1 of PHB were produced when
soybean oil was used as a substrate).
Even if the Cupriavidus genera remains predominant in the production
of PHASCL, other genera were also discovered and studied in recent years:
Bacillus cereus,21 Brevundimonas vesicularis,22 Sphingopyxis macrogoltabia,18
View Online

Bio-based Polymers and Materials 15


OH
glycerol dehydratase 1.3-propanediol oxydoreducatse

OH OH
OH O
OH OH
glycerol 3-hydroxypropionaldehyde NADH + NAD+ 1.3
Published on 11 August 2014 on http://pubs.rsc.org | doi:10.1039/9781782620181-00001

H 2O
propanediol

Figure 1.7 Metabolic pathway for the production of 1,3-propanediol from glycerol.

OH OH

1.3 propanediol

HO2C CO2H

O O
11:50:21.

O n

Figure 1.8 Synthesis of Soronas.

Several studies were accomplished in order to achieve production of PDO


by engineered strains. Two different strategies were attempted: expression of
genes for the glycerol production from glucose in PDO-producing strains
and the expression of the PDO-producing genes in the glycerol-producing
strains. The first strategy was found to be more efficient and has been ap-
plied industrially by Genencor,147–149 a Danisco’s subsidiary.
Further, DuPont performed the polymerization of PDO with terephthalic
acid (Figure 1.8) to obtain Soronas.150
This partially bio-based polymer is mainly used in different fibre appli-
cations such as floor coverings and sportswear. The PDO success story is
considered as an important milestone from both industrial and societal
points of view because it led to the investigation of other possibilities for the
coupling of bio-based and traditional monomers (see below for PBS) with
further consideration of the importance of the bio-based content in poly-
meric materials (controlled by the ASTM D 6866 norm, for example), and to
the ultimate acquisition of Danisco with its Genencor subsidiary by DuPont
in 2011.151
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Nestle Cove post-office, no one claimed the dog. When Mr. Horton
came down the next Saturday and took them all out driving, Curly
perched on Sunny’s lap in the front seat and very plainly enjoyed the
trip.
“He’s used to riding in a car,” said Mr. Horton. “I wonder why no
one advertises for him or tries to find him.”
“Maybe I can keep him always,” said Sunny hopefully. “He can sit
up, Daddy, and beg, and play dead. I think he’s a very educated
dog.”
CHAPTER XII
SUNNY BOY IS NAUGHTY

C URLY proved to be a happy-natured little dog, and was soon a


great favorite with all the children who played on the beach.
“I wish I had one just like him,” said Ellen.
“I’d rather have a bigger dog,” said Ralph. “One, maybe, as big as
Queen.”
“Oh,” declared Sunny Boy, “no other dog could be as nice as
Curly! Though Queen is nice, too, and I like her awful much,” he
added, feeling that if Queen could know what he had just said her
feelings might be hurt.
At first Sunny Boy had an uneasy feeling that the dog might be
claimed any day, but as two weeks went by and no one came to look
for a lost bow-wow, this feeling gradually vanished entirely. “Curly”
was, in Sunny’s mind, his own dog.
“I wish I had something to do,” sighed Sunny Boy one warm
morning.
“Find Ellen and Ralph and play with them,” suggested Mrs. Horton
promptly. She was sitting in the porch swing, mending. Aunt Bessie
and Miss Martinson had gone up to the city to shop.
“Their father took ’em sailing,” Sunny Boy explained
disconsolately, referring to Ellen and Ralph. “I wish Daddy stayed
here all the time. We could go fishing, too.”
“Well, you know what Daddy would say if he were here about little
boys who are always wishing for what they have not,” said Mrs.
Horton, rummaging in her stocking bag for tan cotton to darn a huge
hole in one of Sunny’s socks. “You’ve ever so many pleasant things
to do, dear. Don’t sit there and grumble.”
“I can’t do anything at all!” Sunny Boy was in a perverse mood. “I
can’t go swimming, ’less some one is there watching me. And I can’t
drive the car, ’cause nobody will teach me. An’ you sew all the time
and don’t ’muse me at all!”
Sunny Boy felt so sorry for himself that two big tears ran out of his
blue eyes and splashed down on Curly, asleep in his lap.
“Why Arthur Horton!” Mother’s voice was gentle. “That doesn’t
sound like my little Sunny Boy. Who ever heard of amusing a laddie
with a dog to romp with and the whole beautiful seashore for a
playground? You and Curly run down to the beach now, and see if
you can’t find some more of those shells Aunt Bessie is saving to
make into souvenirs. And this afternoon we’ll go to meet their train
with the car.”
“I don’t want to hunt shells,” grumbled Sunny Boy, kicking his feet
against the step.
“You’ll have to go to your room and stay till lunch time if you can’t
find something pleasant to do,” said Mrs. Horton, firmly. She did not
look at Sunny Boy at all, but at her darning.
Sunny Boy felt as cross as two sticks. He didn’t know why, and
perhaps there wasn’t any reason. If you had asked him, he would
have said that every one was mean to him.
Mother continued to sew steadily. Suddenly a mischievous idea
popped into Sunny’s mind. He put down Curly and ran to his own
room. When he came out he went out of the house the back way,
and slammed the screen-door without speaking to Harriet, who was
busy ironing. You know, don’t you, how it does relieve your feelings
to slam doors? Well, Sunny Boy, who was really as bad as he could
be that morning, felt better directly. He even tried to whistle as he
went down the street.
He knew exactly what he was going to do. He was going to town
and ride on the merry-go-round and have an ice-cream cone. They
had been in Nestle Cove over three weeks, and he had been to town
only that once with Harriet.
“All the other children go,” Sunny Boy said to himself, hailing the
rattling old jitney as it came past the corner. He had taken good care
to walk two blocks down the road so that no one from his house
could see him.
He had a pocketful of pennies that jingled merrily. Daddy on his
last visit had added to the store in the pasteboard box that stood on
Sunny’s bureau, and Mother and the aunties often dropped pennies
in, too. Sunny Boy was sure he had enough money to go to the city
with, had he wished to go.
“Goin’ far?” the jitney driver asked. There were only three other
passengers in his bus.
“To town,” Sunny assured him cheerfully. “Is the merry-go-round
running yet?”
“Well, ’tis, if it didn’t burn down last night,” said the jitney driver. “I
was over that way ’bout ten o’clock, and she sure was crowded.”
The jitney bus went only as far as the post-office, and Sunny paid
his fare there, counting out the five pennies slowly, and jumped
down. He remembered where the merry-go-round was, and if he had
not, the music would have led him to it.
“What are you going on?” asked a boy slightly older than Sunny,
as they stood watching the whirling figures and waiting for the thing
to stop. “I’ve been on everything ’cept the tigers, an’ this time I’m
going on one of ’em.”
“I’d like a zebra,” announced Sunny Boy shyly. “Or maybe a horse
—they go up and down, don’t they?”
“Well, if you’ve money enough, buy two tickets and you can stay
right on for two rides,” advised his new friend. “Let’s see. Oh, yes,
you can buy two. More than two at a time is apt to make you dizzy.
Look, she’s going to stop!”
The merry-go-round did stop with a dismal groan, and Sunny Boy
scrambled on with a crowd of eager children. Most of them had
mothers or older brothers and sisters with them, and when the
attendant came to Sunny Boy and lifted him up, he seemed inclined
to stay there and hold him on.
“I won’t fall off,” urged Sunny with dignity.
“Then you’ll have to be strapped on,” said the man, smiling. “Can’t
have you flying into space when your frisky steed gets to going, you
know. There! now you’re safe, and no one will notice that belt.”
Sunny Boy’s horse went up and down—in time to the
music
Page 161
After the first ride the man came and unbuckled the belt, and,
when Sunny Boy showed his second ticket, lifted him down and up
again on a cream-colored horse. He fastened the belt snugly about
him, and the merry-go-round started gayly. Sunny Boy’s horse went
up and down—in time to the music it seemed to him—and he was
very happy.
When the music stopped and the platform was still, the attendant
came and lifted him down. The floor wobbled under Sunny Boy’s feet
and he felt a bit shaky, but as he walked away he was all right again.
Across the street from the merry-go-round was a large open booth
where soda water was sold. There were people sitting at all four
sides of the fountain and a handsome motor car was drawn up at the
curb before it.
“I’ll get chocolate, with ice-cream,” Sunny Boy decided, jingling his
remaining pennies.
He climbed up, with some difficulty, on one of the high stools, and
gave his order. The white-jacketed boy back of the counter brought it
to him, and with it a pale green check.
“Good, isn’t it?” smiled the white-haired lady who sat next to
Sunny Boy, as he took the first spoonful.
Sunny nodded and smiled, not knowing just what to say.
He had half finished when the boy in the white jacket came back to
him.
“Fifteen cents, please,” he said politely.
Sunny Boy put his hand in his pocket and brought out a little heap
of pennies. He pushed them toward the green check.
“Only eleven cents here,” said the boy impatiently. “Four cents
more, please.”
Sunny Boy looked at him silently, clutching his soda glass tightly
with both hands.
“What is it, dear?” asked the white-haired lady, who was pulling on
her gloves, having finished her soda water. “Haven’t you enough
money?”
Sunny’s lower lip trembled. He shook his head. There was a big
lump in his throat, and he couldn’t have spoken had he tried.
“How much is it? I’ll pay for it,” said the lady, fumbling in her purse.
“Give the child his pennies, and take the check out of this.” She
pushed a bill toward the boy.
“Now drink your soda, dear,” she went on kindly. “Do you live here
in the town?”
“He lives over in the summer colony,” volunteered the boy, bringing
back the change. “My father’s postmaster and he knows every one. I
don’t believe his folks know he’s over here alone. Do they, Buddy?”
Sunny Boy put down his spoon and got off the stool. He didn’t like
to be called buddy, and he had just remembered that his mother
didn’t know where he was. She would worry if he was not home at
lunch time.
“Take your money, kid,” said the boy, who really meant to be kind.
“How are you going to pay jitney fare without a cent in your pocket?
Here, take it.”
Sunny Boy thrust the pennies back in his pocket.
“Thank you very much,” he said to the white-haired lady. “I think
perhaps my mother wants me now.”
The soda fountain boy laughed, but the lady did not. She was very
sweet and serious.
“I wish you’d let me take you home in my car,” she suggested,
quite as one friend to another. “You may have to wait for a jitney
fifteen or twenty minutes, and my chauffeur can have you home in
less time than that. What do you say?”
Sunny Boy nodded, and they got into the beautiful pale gray car,
the tall young chauffeur holding open the door for them. He wore a
gray uniform and the light linen robe he spread over them was gray,
too.
“Curly has hair just like yours,” said Sunny Boy suddenly. He had
been studying the white-haired lady, and he paid her the biggest
compliment he could. He thought Curly’s silky white hair very lovely.
The lady smiled.
“Who is Curly?” she asked.
Sunny Boy told her about the little dog he had found in the storm,
how pretty it was, and how many tricks it could do. The white-haired
lady sat up straighter and straighter, and the prettiest pink came into
her cheeks under her gray veil.
“Carlton, do you hear?” she cried to the chauffeur. “I believe this
child has found Bon-Bon!”
“Bon-Bon?” echoed Sunny Boy, bewildered.
“Yes, Bon-Bon, my dear little dog. My son brought him to me from
France. Is he very tiny, with a sharp little black nose and slim feet? I
thought so! Why you don’t know how glad I am! And to think you’ve
been taking such wonderful care of him all this time!” The white-
haired lady threw her arms around Sunny Boy and hugged him
tightly.
“There he is now,” said the chauffeur, stopping the car before the
Horton bungalow.
Curly, or Bon-Bon as the lady called him, sat on the top step of the
porch, watching them.
CHAPTER XIII
CURLY IS FOUND

T HE white-haired lady was out of the car the instant it stopped


and up the walk, her silk skirts flying in the wind.
“Bon-Bon! Bon-Bon!” she called. Then she said something that
Sunny Boy could not understand. Afterward she told him that it was
French for “Littlest one.”
Curly leaped upon her, barking madly.
The lady took him in her arms and sat down on the step, and, to
Sunny Boy’s amazement, began to cry.
The noise of the dog’s barking brought Mrs. Horton to the door.
“Why, Sunny Boy, where in the world have you been?” she said
quickly. “It’s almost one o’clock. Harriet was just going down to the
beach to look for you.”
Then she saw the strange car at the curb and the strange lady on
her doorstep. The lady stood up and held out her hand.
“I am Mrs. Raymond,” she said. “Colonel Francis Raymond’s wife.
I believe my husband has met Mr. Horton. And now I find your little
boy has found my pet dog.”
Mrs. Horton was very much surprised and greatly pleased to learn
that at last Curly’s own people had been found. She asked Mrs.
Raymond to come in and stay to lunch with them, but Mrs. Raymond
had an appointment at two o’clock several miles away with the
colonel, and lunch would be ready there for the white-haired lady.
She and Mrs. Horton talked very fast, and Sunny Boy could not
understand all they said.
“We advertised and put up a bulletin notice,” he heard Mother say,
“and we couldn’t understand why no one claimed the dog. It was so
evidently a pet, that we knew it couldn’t have been abandoned, and
though exhausted by the storm, it seemed so well-fed we were sure
it had not been lost very long.”
“I lost him the same day you found him,” explained Mrs. Raymond.
“Carlton, the chauffeur, was taking the car up to Draper Inlet to get
my husband. That’s twenty miles up the coast from our cottage, and
Bon-Bon loves so to ride that he never misses a chance to go in the
car. He rode in the back and the hood was down and I suppose he
was on top of that, as he often was. Carlton was trying to make the
inlet before the storm, and I imagine he drove at a pretty hard pace.
Bon-Bon was evidently jolted out going through Nestle Cove, and
neither my husband nor Carlton thought of the dog again till they
reached home and I asked for him.”
“And of course you didn’t know where he was lost,” said Mrs.
Horton sympathetically.
“No, though my husband and Carlton hunted and hunted. But now
everything is all right again. Sunny Boy has made me very happy!”
Mrs. Horton walked with her guest toward the door.
“But what I don’t understand yet,” she said, puzzled, “is how you
met Sunny Boy and he mentioned the dog. Were you out
searching?”
Sunny’s face got very red.
“No, I’d simply stopped in town to get a cool soda before going on
to meet Colonel Raymond,” said Mrs. Raymond. “I think Sunny Boy
had better tell you all about it. Kiss me good-by, dear. I’m going to
send you the very nicest thing I can buy in the city for being so good
to my dog. You won’t feel too bad if I take him away now, will you,
Sunny Boy?”
“No, I—I guess not,” quavered Sunny Boy uncertainly.
He kissed Mrs. Raymond, and gave Bon-Bon, for we might as well
call the dog by its right name now that we know it, a big hug. Then
he sat down on the top step while Mrs. Horton walked with Bon-
Bon’s owner to the car. They stood there several minutes, talking,
and then Mrs. Raymond got in and drove away.
Mrs. Horton came up the path, but Sunny Boy did not look at her.
He was studying a crack in the step with great interest.
“Lunch is on the table, Mrs. Horton,” announced Harriet. “Most
everything’s spoiled, it’s so late.”
“I’m ever so sorry, Harriet, but it couldn’t be helped this time,”
answered Sunny’s mother pleasantly. “Sunny Boy, I want you to go
to your room. Harriet will bring you a bowl of bread and milk, and
when you have eaten that I’m coming in to talk to you.”
Sunny Boy went slowly to his room. When Harriet brought the
bread and milk, he ate it. In perhaps half an hour his mother came
into the room, closing the door quietly.
She drew a low rocking chair near the window where Sunny Boy
stood looking out, and, sitting down, put her arm about him.
“Now tell Mother all about it,” she said, gently turning Sunny Boy
around so that he faced her.
“I wanted to go on the merry-go-round,” explained Sunny Boy,
tracing with his forefinger the outline of one of the pink roses that
grew on Mother’s pretty white dress.
“Well?”
“So I went to town—” Sunny Boy began on another rose.
“And you didn’t ask me? Did you run away, Sunny Boy?”
Sunny Boy was very uncomfortable. His throat didn’t feel right.
And he couldn’t look at his own dear mother, though usually he loved
to watch her face. He wasn’t a Sunny Boy just now.
“Did you run away, Arthur?” she asked again.
Sunny Boy nodded miserably, still fingering the pink roses.
Mrs. Horton did not say anything for a moment. She seemed to be
thinking. Then she gathered both of Sunny Boy’s small hands in her
smooth, soft right hand, keeping her left arm around him.
“Listen to Mother carefully, dear,” she said firmly. “This all
happened because you were cross. Any other morning you would
have found something pleasant to do. But when a little boy makes up
his mind to be cross and not to be pleased with anything he usually
winds up by doing something naughty.”
Two big tears fell out of Sunny Boy’s eyes and rolled down his
cheeks. He was very unhappy.
“What do you suppose Daddy would say,” continued his mother, “if
he knew you had gone over to town without saying a word to me? I
think he would say that he was surprised and grieved to learn that
his only son couldn’t be trusted. Because that is what it really means
—that Daddy and Mother can not trust a little boy who, just because
the day doesn’t go to suit him, runs away and lets his mother worry
about him.”
Sunny Boy put his yellow head down in Mother’s lap and cried as
though his heart would break.
“Don’t you really trust me, Mother?” he managed to sob out.
Mother’s soft arms drew him into her lap.
“Well, yes, I do,” she admitted, smoothing his hair. “Because, you
see, dear, I think you are sorry and will not do it again. Being sorry
makes all the difference in the world.”
Sunny Boy sat up, and this time he found he could look right into
Mother’s deep brown eyes.
“I’m sorry—honest,” he told the little boy he saw there.
“All right, I believe you,” Mother assured him promptly. “I think you
will have to stay here in your room till supper time to help you
remember not to be cross again, and after that we’ll forget about it.
Now tell Mother what you did over in town.”
Sunny Boy told her all about his trip, from the jitney and merry-go-
round rides to his experience at the soda fountain where kind Mrs.
Raymond had paid for his soda-water.
“An’ wasn’t it funny Curly was her dog?” he wound up.
“Yes, indeed,” agreed Mother. “I’m glad the dog found his mistress.
There, I hear the clock striking three. I must go to the station to meet
Aunt Bessie and Miss Martinson.”
“I s’pect they’ll wonder where I am,” said Sunny Boy sadly.
“They probably will,” sighed Mother. “Never mind, Son, just
remember you are never going to run away again.”
And Sunny Boy did remember.
“Why did Mrs. Raymond cry when she found Curly?” he asked, as
Mrs. Horton turned to leave the room. “Did her little boy die in the
war?”
“No, dear,” answered Mrs. Horton. “He came home from France
and brought his mother the dog you call Curly and she calls Bon-
Bon. But her son—he was a Captain—lived only a few months after
he landed in this country; he was invalided home. So, you see, poor
little Bon-Bon means a great deal to Mrs. Raymond because her boy
thought to bring him all the way from France to his mother.”
After Mother had gone—Sunny Boy heard the noise of the car as it
started for the station, though his room was on the wrong side of the
house to see the garage—he thought a great deal about the little lost
dog and the brave soldier who had brought it home to his mother.
The more he thought, the gladder Sunny Boy was to know that Mrs.
Raymond had her dog again.
Two or three days later he was sitting on the front porch waiting for
Aunt Bessie to go swimming with him (Sunny Boy could really swim
very nicely now) when the parcel-post wagon drew up before the
house. The driver grinned as Sunny Boy came flying down the path.
“Package for Arthur Bradford Horton,” he announced cheerfully. “Is
that the little boy who lives next door?”
“Course not!” Sunny Boy was startled at the idea that his package
might go to the boy next door. “That’s my name. Is there something
for me?”
“Looks like it,” admitted the man. “Here you, don’t get under the
horse’s feet, I’m handing it to you as fast as I can. There you are.
Like Christmas, isn’t it?”
Sunny Boy took his package and said “thank you.” It was a large
package, and he wondered what could be in it and who had sent it to
him.
“Maybe it’s from Grandpa,” he told his mother, as she and Aunt
Bessie came out on the porch.
CHAPTER XIV
LOST ON THE OCEAN

“P ERHAPS he has sent you some fresh eggs from the farm,”
teased Aunt Bessie.
“Or a pound of fresh, sweet butter,” suggested Miss Martinson,
coming out on her way to the bathhouse.
“Open it, precious, and see,” urged Mrs. Horton.
So Sunny Boy sat down and carefully untied the red cord and took
off the wrapping paper. There was a pasteboard box tied with more
string to be opened then.
“Why—why—” Sunny Boy, peeping down under the tissue paper
that packed this box, uttered a shriek of delight.
“Look, Mother!” he shouted. “It’s a boat!”
It was a boat, sure enough—a beautiful boat with three sails and
two decks and a large American flag in her bow. Her name was
painted on her sides in bright blue letters—The Billow.
Sunny Boy was delighted.
“Did Grandpa send it?” he asked, his eyes big with surprise.
“I hardly think so,” smiled Mrs. Horton. “See, dear, here is a card
that dropped out. Shall I read it to you? ‘To Sunny Boy, with love
from Mrs. Raymond and Bon-Bon.’ Mrs. Raymond sent it to you,
precious.”
Sunny Boy, of course, wanted to sail his boat immediately. Ellen
and Ralph—Stephen had gone home—who came over presently
thought it was the finest boat they had ever seen. Ralph had one or
two boats, but none as large as The Billow.
“You can sail her sometimes,” offered Sunny Boy. “You get your
Frolic now and let’s go down to the beach and play with ’em. I’ve got
my bathing suit on.”
“If you chickens are going to sail boats, you’ll have to keep away
from the bathing beach,” announced Aunt Bessie decidedly. “You
can’t sail boats in a surf, anyway. Go over on the other side of the
Cove where it is shallow and smoother.”
So the three children, the two boys carrying their boats, marched
over to the side of the Cove where a small fleet of rowboats were
kept at anchor and where the only house in sight was a small shanty
where an old fisherman lived who made his living by selling tackle
and bait.
“Guess Mr. Grimes has taken out a fishing party to-day,” said
Ralph, noticing that the shanty door was closed. “His boat’s gone,
too. Come on now, Sunny, let’s see The Billow race the Frolic.”
The Billow rested lightly on the water, and as there was hardly a
breath of wind, Sunny Boy had to tow her instead of letting her sails
carry her. But towing your boat on a warm summer’s day when you
have your bathing suit on and are not afraid of getting wet, is great
fun.
“If there was any wind, I guess your boat could beat mine,”
conceded Ralph generously. “But if we can’t sail ’em, let’s play taking
fishing parties out.”
“How?” asked Sunny Boy practically.
“Well, we have to have some people—make-believe, of course,”
answered Ralph. “An’ then we ought to have something to eat.”
“Ellen’s paper dolls would do for people,” said Sunny Boy. “We’ll
ask her if she’ll go an’ get ’em. And I’ll go and ask Harriet for
something to eat.”
“All right,” agreed Ralph. “I’ll hold the boats till you come back. Hi,
Ellen!” he called to his little sister. “Want to give your paper dolls a
sail?”
Ellen was willing, when she understood what the boys wanted,
and she trotted up the beach with Sunny Boy to fetch the paper doll
family. At the corner they parted, Sunny Boy to ask Harriet for a
“piece of picnic,” as he said.
“Something to eat?” repeated Harriet in pretended surprise. “Why,
Sunny Boy! Weren’t you here for breakfast? Well, I suppose if you
are going to take a sailing party out, you’ll have to see that they are
fed. How will three of these sandwiches I’m making for supper to-
night do? And three chocolate cup cakes? All right, here you are—
and mind you bring home a fish.”
Ellen came flying down the street with her paper dolls as Sunny
Boy started with his food, and though she eyed the delicious little
cakes hungrily, she waited politely till they had joined Ralph on the
beach.
“Oh, my!” said Ellen’s brother, when he saw what Sunny Boy had
brought. “Gee, I’m hungry! Let’s eat before we take our sailing
parties out, Sunny.”
This suited Sunny Boy, and as Ellen made no objection, the three
children sat down comfortably in the sand and ate every crumb of
Harriet’s goodies.
“And now,” announced Ellen, rising and shaking the short skirt of
her bathing suit free of sand, “Mr. and Mrs. Smith and the seven
Smith children want to go fishing for whitebait.”
This large Smith family were Ellen’s best paper dolls, cut from the
colored fashion plates, and though, as Sunny Boy sensibly said, they
were not exactly dressed for a fishing trip, still they did look as
though they were pleased at such a prospect. Mrs. Smith wore a red
velvet suit and a feathered hat, and her husband was in full evening
dress; three of the girls had silver and gold dresses, two of them
wore skating costumes, and the one boy was wearing his bathrobe.
Ralph said he probably had his bathing suit on underneath, and we’ll
hope he had.
“Let the younger children go on Ralph’s boat,” suggested Ellen,
“and Mr. and Mrs. Smith and their son can go with Sunny Boy.”
She arranged them all neatly, weighted them down with shells so
they would not blow away, and the two boys set off, towing the
boats.
But when they came back from the first trip, there was trouble at
once.
“Where’s Mr. Smith?” demanded Ellen, counting her dolls as soon
as the ships were steadied in the sand.
“Mr. Smith?” echoed Sunny Boy helplessly. “Why—why—isn’t he
there?”
“He isn’t here,” said Ellen coldly. “And the shell that held him down
isn’t here. And, Ralph, where is Lucile?”
Lucile was one of the paper dolls who wore a silver frock.
“Gee! I suppose they’re washed away,” admitted Ralph. “I’m
awfully sorry, honest, Ellen. Sunny and I were watching a boat ’way
out, and we didn’t look back at our ships. I’ll ask Mother to let you
have the new fashion magazine to-night.”
“Well, Mr. Smith was torn in one place,” said Ellen kindly. “And I
never did care so much for Lucile. Daddy always called her cross-
eyed. So you needn’t care, Ralph.”
“What’ll we do now?” asked Ralph, tired of the responsibility of
taking paper dolls sailing. A fellow couldn’t be expected to keep the
silly things from blowing away. “What’ll we do now, Sunny?”
“Yes, what’ll we do, Sunny?” chimed in Ellen.
Sunny Boy could usually be counted on to think of some game. He
played alone so much, and, having no sister or brother, often had to
depend upon himself for amusement.
“We’ll play dry-dock,” he suggested now. “Put our ships up for
repairs, you know. Come on, Ellen, you can help build the dry-dock.”
Sunny Boy had seen pictures of the great dry-docks where ships
were sent to be repaired and painted, and he really had a very clear
idea of how they were used. Naturally, he wasn’t so sure how they
were built, but together he and Ralph and Ellen made an
arrangement of sticks that looked very imposing, and into which they
fitted the Frolic and The Billow with some difficulty.
“I think we’ll take ’em out for another sail,” said Sunny Boy, after
the dry-dock was pronounced finished. “And perhaps we’ll have a
wreck. You stay on shore and signal to us, Ellen.”
“Then we’ll come in and go into dry-dock for repairs! That will be
fun,” agreed Ralph. “Come on, let’s have a big wreck.”
But before they could have a wreck, Ellen called them.
“Look what I’ve found!” she cried.
The boys waded back and tied their ships to a cable that held a
half-sunken scow. Ellen had captured a butterfly, yellow with black
spots, and they watched it flutter its beautiful wings in her hands. It
didn’t seem to want to fly away.
“Perhaps he is a tame butterfly,” suggested Sunny Boy. “Let’s give
him a sail on The Billow.”
He straightened up and looked out to where he had left his boat,
gently rocking on the water. Only Ralph’s Frolic was still tied, and
The Billow was drifting out to sea.
“Ralph!” gasped Sunny Boy. “Look! My boat’s untied!”
He waded into the water, but Ralph, splashing after him, caught
him by his shirt.
“It’s deep out there—the beach goes down,” Ralph explained. “You
can’t catch it, Sunny Boy.”
“Daddy’s coming down to-day and I wanted to show it to him,”
Sunny Boy almost sobbed. “I just have to get it, Ralph. I know! I’ll
row after it. Come on, we’ll take this boat.”
Sunny Boy began to untie the rope that fastened one of the
rowboats.
“Don’t you go, Ralph,” ordered his little sister. “You know Mother
wouldn’t like it. Sunny Boy, you won’t catch your boat, an’ maybe
you’ll be drowned.”
“Won’t neither,” retorted Sunny Boy ungraciously, working at the
stiff rope. “Nobody gets drowned in rowboats—so there!”

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