Spectroscopic Methods in Food

Analysis 1st Edition Adriana S. Franca

Visit to download the full and correct content document:
https://textbookfull.com/product/spectroscopic-methods-in-food-analysis-1st-edition-a
driana-s-franca/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

Multiresidue Methods for the Analysis of Pesticide

Residues in Food 1st Edition Heinzen

https://textbookfull.com/product/multiresidue-methods-for-the-
analysis-of-pesticide-residues-in-food-1st-edition-heinzen/

Spectroscopic Methods for Nanomaterials

Characterization. A volume in Micro and Nano
Technologies Sabu Thomas

https://textbookfull.com/product/spectroscopic-methods-for-
nanomaterials-characterization-a-volume-in-micro-and-nano-
technologies-sabu-thomas/

Microbiological Methods for Environment Food and

Pharmaceutical Analysis Abhishek Chauhan

https://textbookfull.com/product/microbiological-methods-for-
environment-food-and-pharmaceutical-analysis-abhishek-chauhan/

Food Analysis Laboratory Manual 3rd Edition S. Suzanne

Nielsen (Auth.)

https://textbookfull.com/product/food-analysis-laboratory-
manual-3rd-edition-s-suzanne-nielsen-auth/
Phenolic compounds in food : characterization and
analysis 1st Edition Gutiérrez Uribe

https://textbookfull.com/product/phenolic-compounds-in-food-
characterization-and-analysis-1st-edition-gutierrez-uribe/

Hazard Analysis and Risk Based Preventive Controls

Improving Food Safety in Human Food Manufacturing for
Food Businesses 1st Edition Hal King

https://textbookfull.com/product/hazard-analysis-and-risk-based-
preventive-controls-improving-food-safety-in-human-food-
manufacturing-for-food-businesses-1st-edition-hal-king/

Mediations of Disruption in Post-Conflict Cinema 1st

Edition Adriana Martins

https://textbookfull.com/product/mediations-of-disruption-in-
post-conflict-cinema-1st-edition-adriana-martins/

Quantum Dots Applications in Biology 3rd Edition

Adriana Fontes

https://textbookfull.com/product/quantum-dots-applications-in-
biology-3rd-edition-adriana-fontes/

Acrylamide in food : analysis, content and potential

health effects 1st Edition Gökmen

https://textbookfull.com/product/acrylamide-in-food-analysis-
content-and-potential-health-effects-1st-edition-gokmen/
Spectroscopic Methods
in Food Analysis
Food Analysis & Properties
Series Editor
Leo M. L. Nollet
University College Ghent, Belgium

Spectroscopic Methods in Food Analysis (2018)

Edited by Adriana S. Franca and Leo M.L. Nollet

Multiresidue Methods for the Analysis of Pesticide Residues in Food (2017)

Edited by Horacio Heinzen, Leo M.L. Nollet, and Amadeo R. Fernandez-Alba

Marine Microorganisms: Extraction and Analysis of (2016)

Bioactive Compounds
Edited by Leo M. L. Nollet

Flow Injection Analysis of Food Additives (2015)

Edited by Claudia Ruiz-Capillas and Leo M. L. Nollet
Spectroscopic Methods in
Food Analysis

Adriana S. Franca
Universidade Federal de Minas Gerais
and
Leo M.L. Nollet
University College Ghent
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742

© 2018 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-4987-5461-3 (Hardback)

This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made
to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all
materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all
material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not
been obtained. If any copyright material has not been acknowledged, please write and let us know so we may rectify in any
future reprint.

Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized
in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying,
microfilming, and recording, or in any information storage or retrieval system, without written permission from the
publishers.

For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://
www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923,
978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For
organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged.

Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for
identification and explanation without intent to infringe.

Library of Congress Cataloging–in–Publication Data

Names: Franca, Adriana S., editor. | Nollet, Leo M. L., 1948- editor.
Title: Spectroscopic methods in food analysis / [edited by] Adriana S. Franca
and Leo M.L. Nollet.
Description: Boca Raton, FL : CRC Press, Taylor & Francis Group, 2017.
Identifiers: LCCN 2017008762 | ISBN 9781498754613 (978-1-4987-5461-3)
Subjects: LCSH: Food–Analysis. | Food–Quality. | Spectrum analysis.
Classification: LCC TX547 .S638 2017 | DDC 664/.07–dc23
LC record available at https://lccn.loc.gov/2017008762

Visit the Taylor & Francis Web site at

http://www.taylorandfrancis.com

and the CRC Press Web site at

http://www.crcpress.com
 Contents

Preface vii
Editors ix
Contributors xi

PART I FUNDAMENTALS AND INSTRUMENTATION

Chapter 1 Introduction to Spectroscopy 3
David Lee Nelson

Chapter 2 UV–Vis Spectroscopy 35

Suzana Lucy Nixdorf

Chapter 3 Near-Infrared Spectroscopy 69

Ouissam Abbas and Vincent Baeten

Chapter 4 Fourier Transform Spectroscopy 103

Daniel Cozzolino

Chapter 5 Raman Spectroscopy 111

Sagar Dhakal, Jianwei Qin, Moon S. Kim, and Kuanglin Chao

Chapter 6 NMR Spectroscopy 143

Laura R. Cagliani, Paola Scano, and Roberto Consonni

Chapter 7 Fluorescence Spectroscopy 189

Jana Sádecká, Veronika Uríčková, and Michaela Jakubíková

Chapter 8 Ultrasound Spectroscopy in Food Analysis 225

Semih Otles and Vasfiye Hazal Ozyurt

Chapter 9 Instrumentation 237

Didem P. Aykas and Luis E. Rodriguez-Saona

Chapter 10 Multivariate Statistical Analysis and Chemometrics 273

Marcelo M. Sena, Mariana R. Almeida, Jez W. B. Braga, and
Ronei J. Poppi

v
vi Contents

PART II APPLICATIONS
Chapter 11 Food Composition 317
Semih Otles and Vasfiye Hazal Ozyurt
Chapter 12 Food Authentication 327
Cristina Alamprese
Chapter 13 Food Adulteration 353
Daniel Cozzolino
Chapter 14 Food Quality 363
Nikolaos Nenadis, Anna Androulaki, and Maria Z. Tsimidou

PART III FOOD PRODUCTS

Chapter 15 Spectroscopy Analysis of Beverages 429
Daniel Cozzolino and Jessica Roberts
Chapter 16 Nonalcoholic Beverages 435
Basil K. Munjanja and Anna T.D. Gowera
Chapter 17 Novel and Conventional Spectroscopic Study of Cereals and
Cereal Products
Molecular Structure, Chemistry, Imaging, and Nutrition 451
Peiqiang Yu
Chapter 18 Structural Responses of Chemical Functional Groups in
Different Types of Cereal Grains to Heat-Related Processing
Methods Revealed with Advanced Synchrotron and Globar-
Sourced Molecular (Micro) Spectroscopy 463
Yuguang Ying and Peiqiang Yu
Chapter 19 Coffee 485
Adriana S. Franca and Leandro S. Oliveira
Chapter 20 Spectroscopic Methods for Analysis of Edible Oils 509
Xiuzhu Yu
Chapter 21 Dairy Products 543
Basil K. Munjanja and Anna T.D. Gowera
Chapter 22 Fish and Meat 573
María José Ayora-Cañada and Ana Domínguez-Vidal
Chapter 23 Fruits and Vegetables 601
Adriana S. Franca
Chapter 24 Other Food Products 619
Ana Paula Craig and Joseph Irudayaraj

Index 639
 Preface

The determination of product quality and authenticity and the detection of adulteration
are the major issues in the food industry, causing concern among consumers and spe-
cial attention among food manufacturers. The concepts of food quality and authenticity
are quite broad, given the different demands of the manufacturer, consumer, oversight,
and legislative bodies that will ultimately provide healthy and safe products, taking into
account both economic and environmental issues. Given the inherent complexity of food
products, most instrumental techniques (e.g., chromatographic methods) employed for
quality and authenticity evaluation are time consuming, expensive, and labor intensive.
Therefore, there has been an increasing interest in simpler, faster, and more reliable ana-
lytical methods for assessing food quality attributes.
Spectroscopic methods have been extensively employed in the analysis of food prod-
ucts because they often require minimal or no sample preparation, provide rapid and
online analysis, and have the potential to run multiple tests on a single sample (i.e.,
nondestructive). Therefore, this book is dedicated to spectroscopic techniques that are of
relevance to food analysis.
This book is divided into three parts: Part I—Fundamentals and instrumentation,
Part II—Applications, and Part III—Food products. Part I begins with a comprehen-
sive and historic overview of spectroscopic methods (Chapter 1) followed by an exten-
sive discussion on fundamental and theoretical aspects as well as new trends on each
technique (Chapters 2 through 8), instrumentation (Chapter 9), and statistical analy-
sis (Chapter 10). Part II focuses on the specific application of these techniques in food
analysis, dealing with important issues such as composition (Chapter 11), authentication
(Chapter 12), adulteration (Chapter 13), and food quality (Chapter 14). Part III presents
the recent advances in spectroscopy for the analysis of specific food products including
beverages (Chapters 15 and 16), cereals (Chapters 17 and 18), coffee (Chapter 19), edible
oils (Chapter 20), dairy products (Chapter 21), fish and meat (Chapter 22), fruits and
vegetables (Chapter 23), and other food products (Chapter 24).
All chapters have been written by renowned scientists who are experts in their
research fields. We would like to thank all contributing authors and colleagues for their
effort in producing this excellent book. They are the ones who made this project possible.

“As coisas tangíveis tornam-se insensíveis à palma da mão. Mas as coisas findas muito
mais que lindas, essas ficarão.” (Tangible things become insensible at the palm of the
hand. But finished things, more than beautiful, these will stay)

—Carlos Drummond de Andrade

vii
 Editors

Adriana S. Franca, PhD, received her BSc in chemical engineering in 1988 and MSc in
mechanical engineering in 1991 from the Universidade Federal de Minas Gerais, Belo
Horizonte, Brazil. She completed her PhD in agricultural and biological engineering from
Purdue University in 1995.
She is currently a professor in the Department of Mechanical Engineering, the
Universidade Federal de Minas Gerais, Belo Horizonte, Brazil, and also teaches a grad-
uate course on food sciences. She has published 94 articles in international journals,
21 book chapters, and has presented more than 200 research papers at various interna-
tional conferences. Her research areas include food science, sustainable uses of agricul-
tural residues, coffee chemistry, heat transfer, microwaves, and spectroscopic methods.
For more information refer http://lattes.cnpq.br/1719405448685259.

Leo M.L. Nollet, PhD, received his MS (1973) and PhD (1978) in biology from the
University of Leuven, Belgium. He is an editor and associate editor of numerous books.
He edited for M. Dekker, New York—now CRC Press of Taylor & Francis—the first,
second, and third editions of the books entitled Food Analysis by HPLC and Handbook
of Food Analysis. The last edition is a two-volume book. He also edited the Handbook of
Water Analysis (first, second, and third editions) and Chromatographic Analysis of the
Environment, third edition (CRC Press).
With F. Toldrá, he coedited two books published in 2006 and 2007: Advanced
Technologies for Meat Processing (CRC Press) and Advances in Food Diagnostics
(Blackwell Publishing—now Wiley). With M. Poschl, he coedited the book Radionuclide
Concentrations in Foods and the Environment also published in 2006 (CRC Press).
Dr. Nollet has also coedited with Y.H. Hui and other colleagues, several books:
Handbook of Food Product Manufacturing (Wiley, 2007), Handbook of Food Science,
Technology and Engineering (CRC Press, 2005), Food Biochemistry and Food Processing
(first and second editions; Blackwell Publishing—now Wiley—2006 and 2012), and the
Handbook of Fruits and Vegetable Flavors (Wiley, 2010).
In addition, he edited the Handbook of Meat, Poultry and Seafood Quality, first and
second editions, (Blackwell Publishing—now Wiley—2007 and 2012). From 2008 to
2011, he published with F. Toldrá five volumes on animal product-related books, namely,
the Handbook of Muscle Foods Analysis, Handbook of Processed Meats and Poultry
Analysis, Handbook of Seafood and Seafood Products Analysis, Handbook of Dairy
Foods Analysis, and Handbook of Analysis of Edible Animal By-Products. Also in 2011
with F. Toldrá, he coedited for CRC Press two volumes: Safety Analysis of Foods of
Animal Origin and Sensory Analysis of Foods of Animal Origin. In 2012, they both
published the Handbook of Analysis of Active Compounds in Functional Foods.

ix
x Editors

In a coedition with Hamir Rathore, the book Handbook of Pesticides: Methods

of Pesticides Residues Analysis was marketed in 2009, Pesticides: Evaluation of
Environmental Pollution in 2012, and the Biopesticides Handbook in 2015. Other fin-
ished book projects include Food Allergens: Analysis, Instrumentation, and Methods
(with A. van Hengel; CRC Press, 2011) and Analysis of Endocrine Compounds in Food
(Wiley-Blackwell, 2011).
Dr. Nollet's recent projects include Proteomics in Foods with F. Toldrá (Springer,
2013) and Transformation Products of Emerging Contaminants in the Environment:
Analysis, Processes, Occurrence, Effects and Risks with D. Lambropoulou (Wiley, 2014).
In this series, CRC Food Analysis & Properties, he edited with C. Ruiz-Capillas, Flow
Injection Analysis of Food Additives (CRC Press, 2015) and Marine Microorganisms:
Extraction and Analysis of Bioactive Compounds (CRC Press, 2016).
 Contributors

Ouissam Abbas María José Ayora-Cañada

Food and Feed Quality Unit Department of Physical and Analytical
Quality Department of Agricultural Chemistry
Products Universidad de Jaén
Walloon Agricultural Research Centre Jaén, Spain
(CRA-W)
Gembloux, Belgium Vincent Baeten
Food and Feed Quality Unit
Cristina Alamprese Quality Department of Agricultural
Department of Food, Environmental and Products
Nutritional Sciences (DeFENS) Walloon Agricultural Research Centre
Università degli Studi di Milano (CRA-W)
Milan, Italy Gembloux, Belgium

Mariana R. Almeida Jez W.B. Braga

Departamento de Química Instituto de Química
Instituto de Ciências Exatas Universidade de Brasília
Universidade Federal de Minas Gerais Brasília, Brazil
(UFMG)
Belo Horizonte, Brazil Laura R. Cagliani
NMR Laboratory, National Research
Anna Androulaki Council
Freelancer Institute for Macromolecular Studies
Archaiologikou Mouseiou (ISMAC)
Thessaloniki, Greece Milan, Italy

Didem P. Aykas Kuanglin Chao

Department of Food Science and USDA/ARS Environmental Microbial and
Technology Food Safety Laboratory
The Ohio State University Beltsville Agricultural Research Center
Columbus, Ohio Beltsville, Maryland

xi
xii Contributors

Roberto Consonni Michaela Jakubíková

NMR Laboratory, National Research Faculty of Chemical and Food Technology
Council Institute of Analytical Chemistry
Institute for Macromolecular Studies Slovak University of Technology in
(ISMAC) Bratislava
Milan, Italy Bratislava, Slovak Republic

Daniel Cozzolino Moon S. Kim

School of Medical and Applied Sciences USDA/ARS Environmental Microbial and
Central Queensland Innovation and Food Safety Laboratory
Research Precinct (CQIRP) Beltsville Agricultural Research Center
Central Queensland University (CQU) Beltsville, Maryland
North Rockhampton, Australia
Basil K. Munjanja
Ana Paula Craig Department of Chemistry
Department of Agricultural and Biological Faculty of Natural and Agricultural
Engineering Sciences
Bindley Bioscience Center and Birck University of Pretoria
Nanotechnology Center Pretoria, South Africa
Purdue University
West Lafayette, Indiana David Lee Nelson
Pro-Reitoria de Pesquisa e Pós-Graduação
Sagar Dhakal Universidade Federal dos Vales de
USDA/ARS Environmental Microbial and Jequitinhonha e Mucuri
Food Safety Laboratory Diamantina, Minas Gerais, Brazil
Beltsville Agricultural Research Center
Beltsville, Maryland Nikolaos Nenadis
Laboratory of Food Chemistry and
Ana Domínguez-Vidal Technology (LFCT)
Department of Physical and Analytical School of Chemistry
Chemistry Aristotle University of Thessaloniki
Universidad de Jaén Thessaloniki, Greece
Jaén, Spain
Suzana Lucy Nixdorf
Anna T.D. Gowera Departamento de Química
Certification Services Department Universidade Estadual de Londrina (UEL)
Standards Association of Zimbabwe Londrina, Brazil
Harare, Zimbabwe
Leandro S. Oliveira
Joseph Irudayaraj Departamento de Engenharia Mecânica
Department of Agricultural and Biological (DEMEC)
Engineering Universidade Federal de Minas Gerais
Bindley Bioscience Center and Birck (UFMG)
Nanotechnology Center Belo Horizonte, Brazil
Purdue University
West Lafayette, Indiana
 Contributors xiii

Semih Otles and

Food Engineering Department Department of Chemical and Geological
Ege University Sciences
Izmir, Turkey University of Cagliari
Cagliari, Italy
Vasfiye Hazal Ozyurt
Food Engineering Department Marcelo M. Sena
Ege University Departamento de Química
Izmir, Turkey Instituto de Ciências Exatas
Universidade Federal de Minas Gerais
Ronei J. Poppi (UFMG)
Instituto de Química Belo Horizonte, Brazil
Universidade Estadual de Campinas
Campinas, Brazil Maria Z. Tsimidou
Laboratory of Food Chemistry and
Jianwei Qin Technology (LFCT)
USDA/ARS Environmental Microbial and School of Chemistry
Food Safety Laboratory Aristotle University of Thessaloniki
Beltsville Agricultural Research Center Thessaloniki, Greece
Beltsville, Maryland
Veronika Uríčková
Jessica Roberts Faculty of Chemical and Food Technology
School of Medical and Applied Sciences Institute of Analytical Chemistry
Central Queensland Innovation and Slovak University of Technology in
Research Precinct (CQIRP) Bratislava
Central Queensland University (CQU) Bratislava, Slovak Republic
North Rockhampton, Australia
Yuguang Ying
Luis E. Rodriguez-Saona College of Agriculture and Bioresources
Department of Food Science and University of Saskatchewan
Technology Saskatoon, Saskatchewan, Canada
The Ohio State University
Columbus, Ohio Peiqiang Yu
Department of Animal and Poultry
Jana Sádecká Science
Faculty of Chemical and Food Technology College of Agriculture and Bioresources
Institute of Analytical Chemistry University of Saskatchewan
Slovak University of Technology in Saskatoon, Saskatchewan, Canada
Bratislava
Bratislava, Slovak Republic Xiuzhu Yu
College of Food Science and Engineering
Paola Scano Northwest A&F University
NMR Laboratory, National Research Shaanxi, People's Republic of China
Council
Institute for Macromolecular Studies
(ISMAC)
Milan, Italy
 PA RT I
Fundamentals and
Instrumentation
 CHAPTER 1
Introduction to Spectroscopy
David Lee Nelson

CONTENTS

1.1 UV–Visible Spectroscopy 5

1.2 Fluorescence Spectroscopy 6
1.3 Fourier Transform IR Spectroscopy 10
1.3.1 Attenuated Total Reflectance 11
1.3.2 Diffuse Reflectance Infrared Fourier Transform Spectroscopy 12
1.4 NIR Spectroscopy 12
1.5 Raman Spectroscopy 14
1.6 Nuclear Magnetic Resonance 17
1.7 Ultrasound Spectroscopy 20
1.8 Multivariate and Chemometric Analyses 21
1.9 Conclusion 23
References 23

Spectroscopy has had an ever-increasing role in the determination of the composition

and adulteration of foods and beverages. It is important for determining food safety,
accompanying food and beverage production, and for the control of food, beverages, and
packaging in general.
The study of spectroscopy is considered to have begun with Isaac Newton’s experi-
ments with the dispersion of light into its components of various wavelengths with the aid
of a prism (Thomas 1991; James 2007). However, nothing more was studied until the time
of William Wollaston, who improved upon Newton’s experiment in 1802. The dark lines
that appeared in the spectrum (Figure 1.1) were later studied by Joseph von Fraunhofer
(Jackson 2000), followed by Anders J. Angstrom, who measured the wavelengths of these
lines. Fraunhofer also constructed a grating that achieved greater resolution in the disper-
sion of light than the prism (Pasquini 2003). Sir John Herschel studied the spectrum of
flames in 1822 and laid the foundation for spectral analyses. In 1859, Gustav Kirchhoff
suggested that substances emitted and absorbed light at the same wavelength. These and
other studies were the basis of Bohr’s theory of the atom, which specified that electrons
existed in discrete energy levels in the atom (Thomas 1991). August Beer later proposed
the linear relationship between absorbance and concentration, which has since been the
basis for the quantitative determination of substances by measurements of absorbance or
transmittance in the visible and ultraviolet (UV) regions (Thomas 1991).
Electromagnetic radiation consists of electromagnetic waves, which are synchronized
oscillations of electric and magnetic fields that propagate at the speed of light through a vac-
uum. The oscillations of the two fields are perpendicular to each other and perpendicular to

3
4 David Lee Nelson

KH b E D
h g Gf e d h F c h 4-1 3–1 a C B A

390400 450 500 550 600 650 700 750

Wavelength in nm

FIGURE 1.1 Solar spectrum with Fraunhofer lines. (From Gebruiker, M. V. 2005.
Spectrum-sRGB.svg https://en.wikipedia.org/wiki/Fraunhofer_lines.)

Increasing frequency (v)

1024 1022 1020 1018 1016 1014 1012 1010 108 106 104 102 100 v (Hz)

γ-rays x-rays UV IR Microwave FM AM Long radio waves

radio waves

10–16 10–14 10–12 10–10 10–8 10–6 10–4 10–2 100 102 104 106 108 λ (m)
Increasing wavelength (λ)

Visible spectrum
380

450

495

570

590

620

750
V B G Y O R

FIGURE 1.2 The electromagnetic spectrum. (From Ronan, P. and Gringer. 2013. File:
EM spectrum.svg and File: Linear visible spectrum.svg. https://en.wikipedia.org/wiki/
Electromagnetic_radiation.)

the direction of energy and wave propagation, forming a transverse wave. Electromagnetic
waves can be characterized by either the frequency or wavelength of their oscillations, which
determines their position in the electromagnetic spectrum (Crowell 2013). Electromagnetic
radiation involves a wide range of wavelengths, as is shown in Figure 1.2. The electro-
magnetic spectrum refers to all the known frequencies and their linked wavelengths of the
known photons. The electromagnetic spectrum extends from above the long wavelengths
(high frequencies) used for modern radio communication to gamma radiation at the short-
wavelength (high-frequency) end, thereby covering wavelengths from thousands of kilome-
ters down to a fraction of the size of an atom (Mehta 2011). The range of energies involved
in this range of wavelengths varies from 12.4 feV to 1.24 Mev. In principle, the upper limit
for the possible wavelengths of electromagnetic radiation is the dimension of the universe.
The theoretical lower limit is thought to be the Planck length (1.616199(97) × 10 −35 m)
(Bakshi and Godse 2009). Although all the wavelengths shown in Figure 1.2 can be used
for analysis, the range of wavelengths usually employed in spectroscopy is relatively nar-
row and includes mainly the UV, visible, infrared (IR), ultrasound, and FM radio (nuclear
magnetic resonance [NMR]) regions.
 Introduction to Spectroscopy 5

1.1 UV–VISIBLE SPECTROSCOPY

UV light was discovered by J. W. Ritter in 1801 (Thomas 1991). However, there remained
no method by which to measure UV radiation until the development of the photodetector
in the 1930s. The first commercial UV–visible (UV–Vis) spectrophotometer was intro-
duced by Beckman in 1941 (Buie 2011).
The absorbance of light in the UV–Vis region occurs when an electron is excited
and passes from a bonding or nonbonding orbital to an antibonding orbital. The
amount of energy required to excite an electron depends on the difference in energy
between the ground state and the excited state. Transitions of the σ–σ*, σ–π*, π–σ*,
or simple π–π* type require light in the vacuum UV region. However, conjugated π
systems exhibit π–π* transitions that absorb in the region between 200 and 800 nm.
In conjugated systems, the excited state is more greatly stabilized by resonance than
the ground state, so the difference in energy between the two states is smaller than in
nonconjugated systems (Silverstein et al. 1974). The smaller the difference in energy
between the ground state and the excited state, the greater is the probability that a
transition between the ground state and the excited state will occur. The intensity of
the absorbance is a function of this probability. For a given concentration, the inten-
sity of absorbance will be greater when the difference in energy between the ground
and excited state is small. And, this difference will be smaller when there is a greater
degree of conjugation in the molecule.
The nonbonding (n) electrons normally have a higher energy than the ground state
pi electrons. The nonbonding electrons are held less strongly. Therefore, the difference
in energy between the nonbonding orbitals and the antibonding (π*) orbital is small, and
the absorbance corresponding to this n–π* transition occurs at a longer wavelength than
the π–π* transition. However, the nonbonding orbitals are perpendicular to the π* orbit-
als, and there is very little overlap between the two. Therefore, the probability that a non-
bonding electron will be excited to a π* orbital is extremely small, and the intensity of the
corresponding absorbance will also be very low. This transition is said to be “forbidden.”
The absorption bands in the UV–Vis region are very wide. The electronic state is
made up of several vibrational energy sublevels. These different vibrational energy levels
are each composed of several rotational energy levels. The energy differences between the
vibrational levels are much smaller than the differences between electronic energy states
and the differences between rotational energy levels are even smaller. The electronic
excited state also has several vibrational and rotational energy sublevels. Excitation of
the electron involves a transition from any one of the vibrational and rotational levels in
the ground state to any of the vibrational and rotational levels in the electronic excited
state, resulting in several absorptions with small differences in wavelength that form very
wide bands.
UV–Vis spectroscopy has been widely used for the quantitative analysis of substances
that absorb in this region because of the high sensitivity of the method. The UV–Vis
detector has long been employed in chromatography, especially of proteins, and has been
especially useful in high-performance liquid chromatography (HPLC) analysis of many
classes of compounds. It has also proved useful for the qualitative identification of pure
substances, although the quantity of information provided by the UV–Vis spectrum is
much more limited than that of some other spectroscopic techniques. The proposal by
R. B. Woodward (1941, 1942a,b) of a set of empirical rules for calculating the λ max of
the absorbance of unsaturated compounds was an important tool in the identification of
such compounds.
6 David Lee Nelson

A development that increased the usefulness of UV–Vis spectroscopy was the use of
derivatives of the original spectra (Griffiths et al. 1982; Rojas et al. 1988). The first to
fourth derivative of the spectra can be obtained, and this mathematical technique has
been incorporated into the instrumentation. This technique permits the identification and
quantification of mixtures of substances, whereas this identification is much more dif-
ficult or impossible in the original spectrum. This technique has been used in many stud-
ies, such as the determination of tyrosine in proteins (Ragone et al. 1984), the detection
of toxic substances (Gill et al. 1982), the study of the fractions obtained from the partial
hydrolysis of casein and other proteins (Silvestre et al. 1993), and the determination of
phenylalanine in wheat flour (Carreira et al. 2009).
The development of the diode-array detector was especially useful because it became
possible to simultaneously measure the absorbance at several wavelengths, and the spec-
trum could be registered while determining the concentration of the substance eluted from
a column. Another more recent development is the use of diffuse reflectance spectroscopy
for the analysis of substances, including food and nanostructures (Gao and Wachs 2000;
Morales et al. 2007; Rossel et al. 2006; Liu 2016), although this spectroscopic technique
has been more extensively used in the mid- and near-infrared (NIR) regions. Reflectance
spectroscopy does not require modification of the sample and can be applied for qual-
ity control on the production line. This technique is one of the advancements in spec-
troscopy that has been made possible by the development of multivariate analysis and
other chemometric techniques, without which the spectra obtained would make no sense.
Instrumental modifications necessary for the recording of reflectance spectra have also
played a major role in this type of analysis and in the use of microspectroscopy, where
the spectrometer is adapted to a microscope and spectra can be obtained from minute
particles or cells (Les 2010).
When the substance does not absorb significantly in the UV–Vis region, derivatiza-
tion can be performed to obtain a product that does absorb in this region. An example
is the preparation of phenylthiohydantoin (PTH) derivatives of amino acids that do not
have aromatic rings (Nollet and Toldrá 2012). Of course, it is essential that the reaction
be 100% complete.

1.2 FLUORESCENCE SPECTROSCOPY

Fluorescence spectroscopy is a very valuable, highly sensitive technique for determin-

ing the quantity of certain kinds of substances that possess the capability to fluoresce. In
1565, Nicolás Monardes, a Spanish physician and botanist, reported a bluish opalescence
from a water infusion of the wood from a Mexican tree. A Franciscan missionary named
Bernardino de Sahagún observed a similar phenomenon in a wood named “coatli.” Both
woods were reported to have medicinal benefits for the kidney. This type of luminescence
has since been reported in chlorophyll, barium sulfate, quinine, acridine, fluorosceine, and
rhodamine. In 1845, Sir John Frederick William Herschel observed the fluorescence from a
solution of quinine sulfate and termed this phenomenon as “epipolic dispersion.” In 1852,
G. G. Stokes invented the term fluorescence from the mineral fluorspar. He was also the
first person to propose the use of fluorescence as an analytical tool (Chakraborty 2013).
The first fluorimetric analysis was performed by F. Goppelsröder in 1867 for the
quantitative determination of Al(III) from the fluorescence of its morin chelate. Otto
Heimstaedt and Heinrich Lehmann (1911–1913) first developed the fluorescence micro-
scope to investigate the autofluorescence of biosamples such as bacteria, protozoa,
 Introduction to Spectroscopy 7

plant, and animal tissues. Later, the American Instrument Company collaborated with
Dr. Robert Bowman who designed and marketed the first spectrophotofluorimeter (SPF)
in 1956 (National Institutes of Health 2016). Antimalarial research actually initiated
the invention of the SPF as an analytical instrument that can determine the presence of
analytes that fluoresce. The story dated back to 1940, during World War II, when scien-
tists in the United States were required to determine the amount of drug that reached the
malarial parasites in a patient’s blood for a clinical trial of antimalarial drugs. Bernard
Brodie and Sidney Udenfriend of Goldwater Memorial Hospital in New York City
designed a new test using an instrument called a fluorometer that could determine the
amount of the drugs in the blood plasma from the intensity of the fluorescence emitted
from the drug, because many of the drugs used in the trial fluoresce. This observation
helped them to come up with a critical dose of a drug to minimize adverse side effects
(National Institutes of Health 2016).
Normally, only aromatic or highly unsaturated organic compounds fluoresce. One
of the advantages of fluorescence spectroscopy over absorption spectroscopy is the fact
that these compounds can be detected in the presence of substances that do not fluoresce.
Therefore, they can be detected in mixtures without the competition of nonfluorescing
compounds. The technique has several advantages and some limitations. If the compound
to be analyzed does not fluoresce, it must be derivatized or tagged to form a product that
does fluoresce. An example is the detection of polyamines and biogenic amines when they
are separated by HPLC (Ubaldo et al. 2015; Custódio et al. 2015; Kalac and Glória 2009;
Fernandes and Glória 2015). These amines do not fluoresce, so they are treated with
o-phthalaldehyde to produce a fluorescent derivative that can be detected by the fluo-
rescence detector. A 100% conversion to the derivative is necessary. o-Phthalaldehyde,
4-dimethylaminobenzenesulfonyl chloride, 1-dimethylaminonaphthalene-5-sulfonyl
chloride, and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate have also been used
to prepare fluorescent derivatives of amino acids and peptides (Nollet and Toldrá 2012).
In fluorescence spectroscopy, the substance absorbs light in the UV, visible, or NIR
region of the electromagnetic radiation. The electrons are excited from a singlet ground
state to one of several singlet excited states (Figure 1.3). The electron then decays to the

3
Nonradiative
S1 2 transition
1
0

Absorption

Fluorescence
Energy

3
S0 2
1
0
Ground state

FIGURE 1.3 Jablonski diagram showing the intersystem decay and fluorescence after
absorption of light. (From Jacobhed. 2012. Jablonski diagram. https://en.wikipedia.org/
wiki/Fluorescence.)
8 David Lee Nelson

lowest singlet excited state via vibrational relaxation and internal conversion and then
returns to the ground state with the emission of light. Therefore, the wavelength of the
light emitted is longer than the wavelength of the absorbed light. This shift to a longer
wavelength is known as the Stokes shift. The λ max of the light emitted does not shift
with the wavelength of the light being absorbed; only the intensity of the light emitted
is affected because the intensity of the light emitted depends on the number of excited
molecules, and the number of molecules that become excited depends on the wavelength
of the light being absorbed. The spectral range for most fluorescence measurements is
200–1000 nm (Wehry 1997). As with absorption spectroscopy, there is a transition from
the lowest singlet state to a variety of vibrational levels in the ground state, so the emis-
sion band is relatively wide.
Fluorescence spectroscopy is orders of magnitude more sensitive than most other
methods of detection of organic compounds. One of the reasons for the greater sensitiv-
ity when compared to UV–Vis absorption spectroscopy is the fact that any light emitted
is compared to a black background. In absorption spectroscopy, if the concentration of
the sample is very dilute, the difference between the absorbance of the sample and that
of the reference cell will be minimal. That is, the amount of light transmitted will be
nearly the same, and two large values with only a slight difference between them will
be compared. In fluorescence spectroscopy, there is zero light emitted by the reference,
so any light emitted by the sample can be more easily detected. Detection limits down
to 10 −10 mol L −1 or lower can be reached, and extremely small samples can be used. The
sensitivity depends on the quantum yield, which represents the efficiency of the fluores-
cence process. It is defined as the ratio of the number of photons emitted to the number
of photons absorbed. Another important factor is the lifetime of the excited state because
it represents the time available for the excited electron to interact with its environment
(Lakowicz 1999).
An advantage of fluorescence spectroscopy over the UV–Vis absorption technique is
the fact that two frequencies (absorption and emission maxima) are available for iden-
tification of a compound rather than only one. If two sample constituents with similar
absorption spectra fluoresce at different wavelengths, they may be distinguished from one
another by the appropriate choice of emission wavelength. Or, if two compounds have
similar fluorescence spectra but absorb strongly at different wavelengths, they may be
distinguished by proper choice of excitation wavelength (Wehry 1997). When the fluores-
cent spectrum is composed of contributions from a mixture of compounds, synchronized
scanning spectroscopy can be used to distinguish between the components of the mixture
(Sikorska et al. 2005). In synchronized fluorometry, the absorption spectrum and the
emission spectrum are recorded simultaneously with a constant difference in wavelength
between the two.
Another advantage is that the technique is fast and simple and the equipment is
relatively robust so that it can be used in the field for preliminary analyses. It is also
possible to detect emissions remotely if fiber optics or excitation with lasers is employed.
This advantage means that the technique can be used for environmental studies and for
the control of food products during production without the necessity for extraction or
other types of modification of the product. In these cases, filter fluorometers can be used
because the intensity of fluorescence at single excitation and emission wavelengths can be
measured to detect specific analytes without the need for high resolution or array detec-
tors. Portability, low cost, and small size are most important. A large number of photons
can be transmitted by filters, and this characteristic makes them useful for trace analyses.
Laboratory fluorometers usually employ grating monochromators.
 Introduction to Spectroscopy 9

One of the limitations of the use of fluorescence spectroscopy is the fact that the
glassware and solvents utilized must be very clean so that no fluorescent impurities will
interfere with the fluorescence from the sample. Extensive cleanup of mixtures, such as
chromatography, may be required, and this process can be time consuming. Solvents that
absorb in the UV region cannot be used. Another possible interference is the presence of
substances that absorb in the same region in which the analyte emits light, thereby reduc-
ing the quantum yield.
Photobleaching can sometimes occur, especially in the case of fluorescent probes that
might be submitted to radiation over a prolonged period. Photobleaching occurs when a
photolytic reaction causes a rupture in one or more bonds and results in the loss of fluo-
rescence (ThermoFisher Scientific 2016). The last type of interference involves quenching,
which can occur when some substance interacts with the excited state of the molecule and
inhibits fluorescence. The possibility of quenching in mixtures means that care should
be exercised during calibration. Quenching can be caused by collision with another mol-
ecule, such as iodide, oxygen, and acrylamide, or by the formation of a nonfluorescing
complex. This latter type of quenching occurs in the ground state. Quenching can also
occur because of attenuation of the incident light by either the fluorophore or some other
species (Lakowicz 1999).
The lifetime of the excited state can furnish some information regarding its interac-
tions with other molecules in the environment. The lifetime of the excited state might be
sufficiently long so that the solvent molecules can reorient themselves around the mol-
ecule. This relaxation of the solvent is responsible for the Stokes shift caused by the
solvent (Lakowicz 1999). The Stokes shift can indicate whether a protein is folded or if
the fluorophore (tryptophan) is exposed to the solvent water. The shift for a tryptophan
residue buried within the protein molecule will be different from that of a residue on the
surface. Labeling with extrinsic probes can also be used to determine the environment
within a macromolecule.
Fluorescence anisotropy measurements can furnish information regarding the size
and shape of proteins. Fluorescence anisotropy involves the photoselective excitation
by polarized light. Those fluorophores whose absorption transition dipole is parallel to
the electronic vector of the excitation will be preferentially excited. The population of
molecules will be partially oriented, and the light emitted will be partially polarized.
Fluorescence anisotropy can be reduced by rotational diffusion. If the fluorophore is
bound to a large molecule such as a protein or a membrane, rotational diffusion becomes
very limited and anisotropy is more easily observed (Lakowicz 1999).
If the emission spectrum of the fluorophore overlaps with the absorption spectrum of
another molecule, the energy of the excited state can be transferred by resonance without the
emission of light (Lakowicz 1999). The effect depends on whether the two species are free in
solution, covalently linked, or trapped within a membrane or nucleic acid molecule. Resonance
energy transfer can be used to measure distances between sites on a macromolecule.
There are two types of fluorescence measurements: steady-state and time-resolved
measurements. The steady-state measurement is the more commonly used. The time-
resolved measurement measures the rate of decay of the intensity of the emitted light
or the anisotropy. The anisotropic decay furnishes information regarding the molecular
shape and flexibility. The decay in intensity also furnishes information regarding the con-
formation of the molecule or the presence of more than one conformation.
Fluorimetric detectors are widely used in chromatography, especially HPLC, and
in electrophoresis. Capillary electrophoresis is a relatively new technique that achieves
10 David Lee Nelson

a high degree of resolution of the components in the sample. Fluorescence detection is a

very valuable tool for detecting these components.
By employing front-face fluorescence spectroscopy, food samples can be analyzed with-
out destruction of the sample (Karoui et al. 2006; Veberg et al. 2006). It is also a valuable
technique for the analysis of proteins and peptides (Ladokhin 2000), as well as nucleic acids
(Lakowicz 1999; Ono et al. 2012; Suzuki et al. 1997; Behlke et al. 2005; Xiao and Kwok
2003) and for applications such as determining bitterness in beer (Christensen et al. 2005).
Other important subjects include phase-sensitive and phase-modulation resolution of emis-
sion spectra, DNA sequencing, fluorescence sensing, time-resolved protein fluorescence,
excited state reactions, and energy transfer to multiple acceptors (Lakowicz 1999).

1.3 FOURIER TRANSFORM IR SPECTROSCOPY

The existence of IR radiation was discovered by Herschel in 1800 (Herschel 1800a,b).

However, no more interest in this region of the electromagnetic spectrum existed until
absorption spectra were obtained in 1882 by Abney and Festing (1886). They also cor-
related the absorption bands with some functional groups. In 1903, Coblenz (1906) cor-
related the absorbances in the mid-IR region with the vibrations of functional groups.
The recording of IR spectra was difficult until Perkin-Elmer and Beckman developed the
first commercial instruments (Thomas 1991).
Midrange IR spectroscopy was the most extensively employed because of its useful-
ness for the identification of the vibrations of functional groups in pure compounds.
In addition, the supports for liquids and solids were inexpensive and easily prepared.
The technique was highly valuable as a tool for use in the identification of compounds.
It could be used for the identification of liquids using films supported between sodium
chloride plates. Spectra of solids could be obtained in solution, in the form of a mull or
as a suspension in a KBr pellet. The technique measured the IR light transmitted through
the sample. The resulting spectra were not exactly reproducible because the concentra-
tion of the sample and conditions were difficult to reproduce exactly. In addition, for
aqueous solutions or humid samples, the supports used needed to be insoluble in water.
Also, the IR bands corresponding to water interfered with some of those obtained with
organic compounds such as alcohols, amines, and amides. The use of midrange IR trans-
mission spectroscopy for the study of pure compounds is very useful, but for the study of
foods, it is somewhat limited because of the complexity of the matrices. The energy levels
involved in these vibrations are low (2.5–25 μm wavelength). For the vibration to result
in an absorption band in the spectrum, the vibration must cause a change in the dipole
moment of the molecule.
There are basically two methods by which one can obtain the IR absorption spec-
trum. The original IR instruments were of the dispersive type. These instruments sepa-
rated the individual frequencies of energy emitted from the IR source by the use of a prism
or grating, and a few wavelengths at a time passed through a slit and then through the
sample. The grating is a more modern dispersive element that furnishes a better resolu-
tion of the frequencies of IR energy. The detector measures the amount of energy at each
frequency that has passed through the sample. This results in a spectrum, which is a plot
of intensity versus frequency or wavelength. This method is slow. Because of the necessity
for the light to pass through a slit, part of the energy transmitted by the sample is lost.
The second method is called Fourier transform infrared (FTIR) spectroscopy. In this
method, the light that impinges on the sample is composed of all of the wavelengths, and
 Introduction to Spectroscopy 11

the computer transforms the signals of all of the transmitted wavelengths into a spectrum
using a mathematical technique, the Fourier transformation. Instead of a prism or grat-
ing, an interferometer is used. The spectrum is obtained in a few seconds instead of a few
minutes. After passing through the interferometer, the beam passes through the sample
and impinges on the detector. The signal that is measured is digitized and sent to the com-
puter where the transformation takes place. FTIR still involves the transmission of light
through the sample and, thus, suffers from some of the same limitations that dispersive
instruments possess (Thomas 1991; Blum and John 2012).
This technique has been used for the study of proteins and protein–ligand interactions
(Jung 2000). It has also been used for the characterization of spoilage fungi (Shapaval
et al. 2013) and for the study of phospholipids in edible oils (Meng et al. 2014). Other
examples of the use of FTIR for the analysis of foods include its use for the determination
of thermoxidized olive oil (Tena et al. 2013), the study of defective and normal coffees
(Craig et al. 2012), the detection of H 2O2 in food (Şansal and Somer 1999), the study of
the secondary structure and conformation changes in polyphenol oxidase (Baltacioğlu
et al. 2015), and the detection of adulteration in food (Rodriguez-Saona and Allendorf
2011).

1.3.1 Attenuated Total Reflectance

Although transmission measurements are used, the diffuse reflectance measurements have
proved to be much more useful for the analysis of food. New techniques of surface analy-
sis (Chabal 1988) and reflectance analysis (NUANCE 2016) have been employed. These
techniques facilitate the monitoring of foods during the production process without the
destruction of the sample. Thus, the detection of adulteration and the determination of
the quality of the product can frequently be accomplished more rapidly. The technique is
called attenuated total reflectance (ATR). It is a sampling technique used in conjunction
with IR spectroscopy that enables samples to be examined directly in the solid or liquid
state without further separation and purification (Carter et al. 2010). In this aspect, it is
similar to Raman spectroscopy (RS) (Mauricio-Iglesias et al. 2009).
A beam of IR light is passed through an ATR crystal so that it reflects at least once
off the internal surface in contact with the sample. This reflection forms an evanescent
wave, which extends into the sample to a depth of 0.5–2 μm with each reflection along
the top surface (NUANCE 2016). The exact value is dependent on the wavelength of the
light, the angle of incidence, and the indices of refraction for the ATR crystal and the
medium being probed (Minnich et al. 2010), the efficiency of sample contact, the area of
contact with the sample, and the crystal material (SpectraTech 2000).
The number of reflections can be varied by varying the angle of incidence. The beam
is collected by a detector as it exits the crystal. Most modern IR spectrometers can be
converted to ATR by mounting the ATR accessory in the spectrometer’s sample compart-
ment (WOW 2016; Sawant 2016).
The sampling surface is pressed into intimate contact with the top surface of a crys-
tal such as KRS-5, ZnSe, or germanium. To obtain internal reflectance, the angle of
incidence must exceed the critical angle. This angle is a function of the refractive indices
of both the sample and the ATR crystal. The evanescent wave decays into the sample
exponentially with distance from the surface of the crystal over a distance on the order of
micrometers. The depth of penetration of the evanescent wave is defined as the distance
from the crystal–sample interface at which the intensity of the evanescence decays to 1/e
12 David Lee Nelson

(37%) of its original value. Different crystals have different refractive indices because of
the crystal material. Different crystals are applied to different transmission ranges (ZnSe
for 20,000–650 cm−1 and Ge for 5500–800 cm−1) (NUANCE 2016; Sawant 2016). In
a spectrum obtained by transmission, the path length is the thickness of the sample. In
ATR, the effective path length (EPL) can be calculated as

EPL = penetration depth × number of reflections.

The EPL is directly related to the absorbance intensity. An increase in either the depth
of penetration or in the number of reflections will increase the absorbance intensity of
the spectrum. The penetration depth of the IR energy into the sample is proportional
to the wavelength. In other words, the depth of penetration decreases when the wave-
number increases. Thus, the relative band intensities in the ATR spectrum decrease with
increasing wavenumbers when compared to a transmission spectrum of the same sample
(SpectraTech 2000; Suraj 2013).
Examples of the use of ATR include the study of the structure, orientation, and
tertiary structure changes in peptides and membrane proteins (Vigano et al. 2000),
the study of the structure of potato starch (van Soest et al. 1995), the drying process
of sodium alginate films (Xiao et al. 2014), and the determination of linoleic acid in
potato chips (Kadamne et al. 2011). Micro-ATR IR spectroscopy has also been investi-
gated (Suraj 2013). ATR-IR has been applied to the microfluidic flow of aqueous solu-
tions in microreactors (Greener et al. 2010) or in flow cells (Carter et al. 2010; Minnich
et al. 2010).

1.3.2 Diffuse Reflectance Infrared Fourier Transform Spectroscopy

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) is a technique that

collects and analyzes scattered IR energy. It is used for measurement of fine particles
and powders, as well as rough surfaces (NUANCE 2016). When an IR beam enters the
sample, it can either be reflected off the surface of a particle or be transmitted through a
particle. The IR energy reflecting off the surface is usually lost. The IR beam that passes
through a particle can either reflect off the next particle or be transmitted through the
next particle. This transmission–reflectance event can occur many times in the sample.
The scattered IR energy is focused onto the detector. The IR light is partially absorbed
by the sample particles, and this absorption yields information regarding the sample. In
the case of colloids and particles in suspension in a volatile solvent, the solvent can be
evaporated and the spectrum obtained on the residue (NUANCE 2016).

1.4 NIR SPECTROSCOPY

The NIR and far-IR regions of the spectrum originally furnished much less information
about the composition of material because of the wide, overlapping peaks and weak
absorbance. NIR began to be employed in 1938, but its use only took hold in the 1980s.
The first work on the analytical exploitation of the NIR spectral region involved the
determination of the amount of water in gelatin by employing its absorption in the NIR
region (Ellis and Bath 1938). Barchewitz was the first to apply NIR spectroscopy for the
analysis of fuel (Barchewitz 1943). Other studies were performed in the 1950s (Evans
 Introduction to Spectroscopy 13

et al. 1951; White and Barrett 1956; Whetsel et al. 1958) on the use of NIR for the study
of mixtures and its obedience to Beer’s law (Pasquini 2003). NIR spectroscopy is a type
of vibrational spectroscopy that employs photon energy (hν) in the energy range from
2.65 × 1019 to 7.96 × 1020 J, which corresponds to the wavelength range from 750 to
2500 nm (Pasquini 2003).
The technique has various advantages: It is fast, nondestructive, and noninvasive,
and requires very limited sample preparation. The radiation is highly penetrating and
can be used for analyses on the production line. Nearly any molecule containing CH,
NH, SH, or OH bonds can be detected. Because of its high penetrability, which allows
the detection of substances within the upper layers of tissue, NIR has been employed
for the study of the brain and muscle physiology (Ferrari and Quaresima 2004). Several
constituents can be measured simultaneously (Osborne 2006). However, because of the
large number of wavelengths and absorbances that must normally be computed, the tech-
nique requires the use of chemometric techniques and computer control and analysis. It
also requires good standards that are adequate for defining the data points that should
be measured. It is a secondary method of analysis. A primary method is required to fur-
nish the analytical results necessary for modeling of the NIR spectral data. The model
may be very complicated and may need to be updated frequently because of changes in
the sample matrix. Robust models might require that many samples be analyzed by the
primary method. Also, the technique is not very sensitive; the limit of determination is
approximately 0.1% (Pasquini 2003).
Although absorption measurements are used, the diffuse reflectance measurements
have proved to be much more useful for the analysis of food. New techniques of surface
analysis (Chabal 1988) have been employed. These techniques facilitate the monitoring
of foods during the production process without the destruction of the sample. Thus, the
detection of adulteration and the determination of the quality of products can frequently
be accomplished more rapidly. The NIR region is composed principally of overtones and
combination bands corresponding to absorptions in the mid-IR region, as well as the NIR
region. The bands observed in the NIR region are weak and generally poorly resolved.
Each successive overtone band is approximately an order of magnitude less intense than
the preceding one. Thus, several choices of absorptions of different intensity contain-
ing the same chemical information are available. Because water absorbs weakly in this
region, high-moisture foods can be analyzed (Osborne 2006).
The first type of instrument employed was the dispersive type, which used diffraction
gratings. These instruments were used in the early days of NIR spectroscopy and are still
being used. They are of relatively low cost compared with other NIR instruments. The
main disadvantages of dispersive instruments are the slow scan speed and a lack of wave-
length precision, which deteriorates during long-term operation because of mechanical
fatigue. Also, the presence of moving parts limits the use of dispersive instruments in the
field. However, the development of linear sensor arrays allows the entire spectrum to be
scanned in a few seconds, and the lack of moving parts in such instruments means that
the dispersive optics have a longer lifetime.
The NIR instruments may use filters to determine the wavelengths to be detected.
These instruments are more limited with respect to the range of wavelengths available, but
are less expensive and are used mostly for measuring the quantities of specific substances
such as water, proteins, and fats. They are usually more robust and have found use in the
field or in the online control of production (Morimoto et al. 2001). NIR instruments that
use filters are more robust because the optical parts are not harmed by environmental
humidity. The detectors for the NIR spectral region are usually based on silicon, PbS, and
14 David Lee Nelson

InGa. The last has a high sensitivity and response speed. When high-powered radiation
sources are used, these detectors can impart a very high signal-to-noise ratio.
Light-emitting diode (LED)-based instruments can produce NIR radiation with a
bandwidth of about 30–50 nm, centered in any wavelength of the spectral region. The
instruments can employ a set of LEDs as sources of narrow NIR bands (Ellekker et al.
1993; Evans et al. 1993) or use them to produce a polychromatic, highly stable source
whose radiation is dispersed by using common monochromator devices such as those
based on gratings or filter optics (Goto 1989). The LED and filter instruments are of
lower cost, they are smaller, and they can be more adequate for use in the field (Pasquini
2003).
The fourth type of instrument is based on acousto-optic tunable filters (AOTFs) (Abe
et al. 1996). Such instruments utilize a technology that involves no moving parts. They
are capable of very high speeds over a wide range of the spectral region. The scan speed
is very fast, and random access to a large number of frequencies is possible.
The type of spectrophotometer of choice for research utilizes the interferometer and
Fourier transform to convert the intensities of the individual frequencies. These instru-
ments possess the highest precision and accuracy of wavelength, a high signal-to-noise
ratio, and a high scan speed, although they are slower than AOTF-based instruments
(Kays and Barton 2003). These instruments do not have entrance or exit slits that can
limit the intensity of the radiation reaching the detector. The wavelength accuracy is
better than 0.05 nm and the resolution can reach values below 1 nm in the NIR region.
However, the instruments are more expensive than the dispersive or filter types, and they
are less robust than the filter or AOTF-based instruments.
Some of the applications of NIR spectroscopy include agricultural products, indus-
trial food products, precision agricultural or soil analyses, polymer processing, polymer
quality characteristics, fuel quality control, fuel production processes, petroleum, envi-
ronmental analyses, textiles, biomedical or clinical analyses, pharmacy and cosmetics,
and NIR imaging (Williams and Norris 1987; Pasquini 2003). NIR spectroscopy is used
routinely for the compositional, functional, and sensory analysis of food ingredients,
process intermediates, and the final products (Pasquini 2003).
NIR spectroscopy has been used to determine protein content (Kays et al. 2000) and
soluble and insoluble dietary fiber (Kays 1998; Kays and Barton 2002) in cereal foods and to
predict gross energy and usable energy (Kays and Barton 2003). Evans et al. (1993) utilized
NIR spectroscopy to determine the authenticity of orange juice. It has also been employed to
determine the protein and lactose contents of goat’s milk (Diaz-Carrillo et al. 1993) and the
protein, casein, and fat contents in cow’s milk (Laporte and Paquin 1999). Studies of starch
and water in cereal food products have been performed (Osborne 1996). The control of the
variation in water content of foods (Wahlby and Skjoldebrand 2001) is another application.

1.5 RAMAN SPECTROSCOPY

Chandrasekhara Venkata Raman discovered Raman radiation in 1928 using sunlight

as the source, a telescope as a collector, and his eye as the detector. Later, lamps using
helium, bismuth, lead, zinc, and mercury were tested, and the mercury lamp was adopted,
followed by the mercury burner and the mercury arc. Other types of lamps were studied,
but in 1962, the laser source was developed (Ferraro et al. 2003). Photographic plates
were first used as detectors until the photomultiplier tube was developed after World
War II. Double and triple monochromators were introduced to reduce stray light. Fourier
Another random document with
no related content on Scribd:
export of cotton to so considerable an amount. I found the best-
informed opinion in Southern Nigeria imbued with the belief that the
1911 crop will be a poor one, though better than last year’s, but that
the prospects for the crop of 1912 are good. The newly opened
ginnery at Oshogbo is said to be doing well. The ginnery at Oyo,
however, is apparently lying idle. At any rate, it had done nothing, I
was there informed, ever since it was put up, some four years ago. A
good deal seems to have been spent upon the experimental
plantation at Ibadan, with indifferent results. It has now been taken
over by the Government, whose officers, I was informed, found it in a
very neglected condition.
Personally, I do not attach, in a sense unfavourable to the growth
of the industry, much importance to the drop in the output. The field,
it must always be remembered, is small, the entire Western Province
being only 27,640 miles square, and much of it, as already stated,
covered with forest. In West Africa new industries are always liable
to violent fluctuations. The drop in the maize export is much more
considerable than the falling off in cotton. Unfavourable seasons, too
much rain or too little, late sowing, and other considerations play a
determining part in these matters. Things move very slowly in West
Africa as a rule. The cotton crop is not the easiest to handle.
Compared with ground nuts, for instance, it entails a great deal more
time and trouble. All kinds of obstacles have to be encountered and
overcome which people at home have difficulty in fully appreciating.
The experimental stage of any enterprise, especially in a place like
West Africa, is bound to leave openings for error, and error in West
Africa is a costly luxury. The Protectorate is under considerable
obligations to the Association for the good work it has done and is
doing.
It seems to me that the British Cotton-growing Association may
perhaps find it advisable, so far as the Western Province of Southern
Nigeria is concerned, to reconsider two aspects of its policy.
Fundamentally that policy is without question sound—viz. the
recognition that agricultural development in West Africa can only be
possible on any scale worth mentioning when undertaken by the
natives themselves. A policy of large plantations run under white
supervision by hired native labour will not pay in West Africa, and,
politically speaking, is virtually impossible. The Association should
receive public support in resisting any pressure which might be
placed upon it to alter its fundamental policy by those of its
supporters who may be impatient of a comparatively slow advance—
slow, i.e., in comparison with the unwise optimism displayed by
some of the Association’s friends upon public platforms. I doubt,
however, if an export trade in cotton will ever reach substantial
proportions—let us say 100,000 bales per annum twenty years
hence—in the Western Province unless the element of competition is
introduced. Hitherto, by combining with the merchants, the
Association has established a fixed buying price. In the initial stages
this was a good thing. The native farmer wanted the certainty that his
crop would be purchased if he were induced to grow it. Now that the
industry is well on in its stride it may be seriously questioned whether
the Yoruba farmer, the certainty of sale notwithstanding, will be
content with the prices offered him under the monopoly agreement
now obtaining. He has always the oil palm to fall back upon; but he
has, in addition, cocoa and maize. Cocoa is rapidly increasing, and
the profit realized by the cultivator is a good one. The timber trade,
too, is growing slowly, and the forest is always yielding fresh
elements of trade. The bulk of the cotton produced in the Western
Province to-day is roughly similar to “middling American,” which is
now quoted, I believe, at 8d. a pound, but some of the Yoruba cotton
fetches up to 3d. above “middling American.” It is asserted by the
Association that 4 lbs. of seed cotton are required in the Western
Province to produce 1 lb. of lint. The native cultivator is (now)
supposed to get from the combine—i.e. from the Association and the
merchants, as the case may be—from 1d. to 1⅛d. per lb. of seed
cotton. I say “supposed,” because I was informed that the actual
producer had not always got the amount which he was understood to
be getting. As regards Northern Nigeria, until the close of last year
the native had never been paid 1d. a lb. cash, and I was given to
understand that conditions had been much the same in the Southern
Protectorate, except at Ilushi, where it was proved to my satisfaction
that the amount of 1d. cash had actually been paid.
 The Association reckons, I understand, that at this rate every
pound of lint landed in Liverpool costs the Association 6½d. I cannot
check that figure. I merely quote it. But one may point out that in
addition to the profit at the present price of “middling American”
disclosed by this estimate, there must be a considerable profit to the
Association on the seed, which, upon arrival in England, is worth, I
believe, between £5 and £6 per ton. Moreover, as already stated,
some of this Yoruba cotton is fetching a higher price than “middling
American,” and I do not think it is beyond the mark to say that, but
for the fact that the Association’s ginneries are not continuously
employed, the Association’s profits on Southern Nigerian cotton to-
day would be substantial. It must be fairly obvious from what
precedes that if the industry were placed upon an ordinary
commercial footing like any other, with merchants competing on the
spot for the raw material, the Yoruba farmer would have no difficulty
in obtaining very much more than he gets at present for his crop.
Cultivation, under those circumstances, would become
proportionately more profitable and a greater acreage would be laid
out in cotton. No doubt it would cut both ways, the native restricting
his acreage when the price fell, but it may be fairly argued that no
special reason now exists for treating the cotton industry on an
artificial basis, that it must take its chance like any other, and like any
other become subject to ordinary economic ups and downs. We
cannot expect the native farmer to concentrate upon one particular
crop if he can make a greater profit in cultivating another. No industry
can develop healthily on artificial lines. If this suggestion were
thought worthy of consideration, the Association’s rôle could be
confined to ginning, and, if asked to do so, selling on commission, or
that rôle might be combined with buying and selling in cases where
the producers preferred to deal with the Association, or found it more
convenient to carry the cotton direct to the various ginneries. That,
no doubt, would force the Association into competition with the
merchants, and the merchants, bringing out their own gins (if it paid
them to do so), might cause the Association’s position to become
precarious. The first alternative would, therefore, appear the most
desirable, the merchants being the buyers and the Association, the
ginners, and, if necessary, sellers on commission. Each force would
then be operating within its natural orbit, and an unnatural alliance
would cease, unnatural in the sense that one price means one
market, and that one market is not an inducement to economic
expansion, especially when the price of other tropical products
produced by the Yoruba farmer with an open free market to deal in
has been steadily rising during the last few years. The Association
has always contended that its primary object is not money making,
but the establishment in our oversea dependencies of an Imperial
cotton industry calculated in the course of time to relieve Lancashire,
in whole or in part, of her dangerous dependence on American
speculators.
The other point which those responsible for the management of
the Association might conceivably think over, is one that impressed
me in Northern Nigeria when inspecting the beautifully kept cotton
plantations in the Kano and Zaria provinces. I was later on to find
that it was one upon which very strong, though not unanimous,
opinions were held by persons of experience and judgment in the
Southern Protectorate. A great deal of energy, and doubtless money
too, is apparently expended by the Association in experimenting with
and distributing seeds of non-indigenous varieties of cotton. Now,
although one cannot say without careful cultivation, speaking of the
north, one can at least say without perpetually improving scientific
cultivation extending over a century, Nigeria is able to produce
indigenous cotton, fetching to-day 1¼d., 2d., and even 3d. per lb.
above “middling American.” Does not this fact constitute the
strongest of pleas for concentrating upon the improvement of the
indigenous varieties instead of distributing effort by worrying about
the introduction of exotics? If these indigenous plants, without a
century’s scientific care, can produce cotton superior in value to
“middling American,” what could they not do with a tithe of the
attention which has been lavished upon the industry in the States? I
know the experts will argue that the indigenous varieties make a lot
more wood, and that an acre planted with American varieties will
yield much more lint than an acre planted with a Nigerian variety. Not
being an expert I would not venture to dispute this. All that I would
make bold to query would be whether experiments tending to prove
it have in Nigeria been sufficiently continuous and carried out under
conditions of fairness to the indigenous cotton sufficiently conclusive
to place the matter beyond the pale of discussion. Even if this were
so, I am not sure that it could be taken as an irrefutable reply to the
contention I have ventured to put forward. For, on the other side,
must be reckoned the diseases which invariably attack all exotics,
animal, vegetable, and human, introduced into the West African
forest region. At every halt on my trek from Riga-Chikum to Kano, a
matter of twelve days, wherever I saw cotton plantations, and often
enough at points on the road, I made it my business whenever
practicable to put a number of questions to the Sarikis (chiefs) and to
individual farmers on the subject of cotton-growing. I always
prefaced these questions with an assurance that I did not belong to
the Government and that I was not a commercial man, but merely a
Mallam (I believe my interpreter sometimes inserted on his own
account the word “wise” before Mallam), who travelled about and
wrote “books,” and that my friends could therefore feel satisfied that
they would not be causing me any pleasure at all by answering my
questions in any particular manner—that, in short, I did not care a
row of yams what their answer might be. One question I never failed
to ask was whether the Government had distributed seed to that
particular village or in that particular area, and if so, what result had
followed the sowing of it? Sometimes the answer was in the
negative. When it was in the affirmative it was invariably the same.
The Government seed had come. It had been sown. But it was “no
good.” Now, I disclaim all attributes of wisdom in this matter of
cotton. But I beg you to believe me when I say that the Hausa farmer
is no fool.[14]
 CHAPTER III
THE COTTON INDUSTRY—continued

Cotton is grown extensively in parts of Northern Nigeria, not for

export—outside the Hausa provinces—but for home consumption. In
Kano province—28,600 square miles in extent with 2,500,000
inhabitants, more than one-fourth of the total population of the
Protectorate—its cultivation is accompanied by what can, without
exaggeration, be termed a national industry of weaving,
manufacturing, embroidering, and dyeing the garments, both under-
garments and over-garments, which the Kano people wear. But not
the Kano people alone. For many centuries, for nearly 1000 years
probably, the Kanawa have been famed throughout the great region
comprised between the bend of the Niger and the ocean as the
expert cotton manufacturers of Africa; the most interesting region in
all the Dark Continent, where divers races have ceaselessly
intermingled, attracted thither by its fertile soil and abundant
pastures; Libyan and Berber, Egyptian and Semite, and the
mysterious Fulani. Three-fourths of the “men of the desert,” too, the
fierce-eyed, black-lithamed Tuareg, descendants of the Iberians,
who roam over the vast spaces between Tripoli and the Chad,
replenish their wardrobes from the Kano looms. Throughout Bornu,
Wadai, and Baghirmi, in the northern German Cameroons as far east
as Darfur, Kano cloths hold unquestioned sway. The Kanawa are not
the only Nigerians who manufacture cotton goods; but they are the
only people among whom the industry may be truly called a national
one. As carried out in Kano province this industry adds dignity,
interest, and wealth to the life of the people, assists their inventive
faculties, intensifies their agricultural lore, and sustains several other
branches of industrial activity, binding in close alliance of material
interest the agriculturist and the artisan. It gives a healthy, attractive
employment to many thousand homes—employment carried on in
the free air of heaven, beneath the bright sunshine of Africa. It has
become a part of the national life, the pride and profit of the people.
Men, women, and children participate in it, the men clearing the
ground, hoeing and sowing, the women and children doing the
picking, the women cleaning the lint of the seeds (on flat stones),
teasing, the men weaving, tailoring, and usually, but not always,
embroidering. Woven in long, narrow strips, the manufactured article
is of remarkable durability and firmness of texture. The
predominating dye is the blue of the indigo plant, extensively
cultivated for the purpose, dyepits being common all over the
province. The embroidery, both in regard to design and execution, is
astonishingly handsome, and the colours harmoniously blended. A
fine specimen of a finished riga—the outer robe covering the
shoulders, with an aperture for the head and neck, and falling in
folds to the knee—is a work of art of which any people in any country
might be proud. It is a very heavy garment, and it is costly. But it is
suitable for the cold nights and chilly mornings, and it lasts for years.

WOMEN COTTON SPINNERS.

 MEN WEAVING.

It is impossible to separate the cultivation of cotton from the

agricultural pursuits of the people generally. Cotton, like cassava,
onions, ochro, pepper, ground nuts, and beans, takes its place as
one of the secondary crops. The people are primarily a people of
agriculturists, raising vast quantities of cereals year after year for
home consumption and export to other districts—guinea-corn and
millet, yams, maize, a little wheat. In the Kano Emirate or division—
as distinct from what is known as the Kano province—the population
is exceedingly dense, and virtually the whole land is under
cultivation. I have seen nothing more remarkable in the way of
cultivation either in France or Flanders. And it is all done with the
galma, a peculiar kind of short-handled hoe, which would break the
back of an English labourer to use, but which the Hausa will wield for
hours together. The pattern of the galma is of great antiquity. It came
from ancient Egypt, with the original inhabitants probably; the
plough, which was used in Egypt when intercourse was frequent
between the valleys of the Nile and Niger, never seems to have
penetrated so far West—a curious and unexplained fact.
 Long, deep, broad, parallel ridges cover the surface of the land,
dotted here and there with magnificent specimens of the locust-bean
tree, the shea, the tamarind, and many other varieties, under whose
shade it seems a favourite device to grow a catch crop of pepper.
How does the soil retain, year after year, its nutritive properties? That
is the secret of the Kanawa, who from generation to generation have
studied it in conjunction with the elements, as the Niger pilots have
learned to read the face of the waters and can steer a steam launch
where no white man could without running his craft upon a
sandbank, especially at low water. That they have acquired the
necessary precise knowledge as to the time to prepare the land for
sowing; when to sow and how to sow; how long to let the land lie
fallow; what soils suit certain crops; what varieties of the same crop
will succeed in some localities and what varieties in others; how to
irrigate the land situate in the vicinity of the waterways and planted
with secondary crops in the dry season; how to ensure rotation with
guinea-corn, millet, ground nuts, and beans; when to arrange with
the Fulani herdsmen to pasture their cattle upon the land—so much
at least the outsider interested in agricultural problems can gauge to
some extent. For miles and miles around Kano city one passes
through a smiling country dotted with farms, riven by fine, broad
native roads lined with hedges of euphorbias and other plants.
Great care is lavished upon the cotton and cassava plantations—
the two chief secondary crops. When the cotton fields are in the
neighbourhood of a road, and very often when they are not, they are
surrounded by tall fencing, eight to ten feet in height, usually
composed of reeds and grass or guinea-corn stalks, to protect them
from the depredations of cattle, sheep, and goats, all of which
abound. In April and May, with the advent of the early rains, the land
is cleared and hoed into furrows and ridges. Along the ridges drills
are made at a distance of two and a half to three feet apart, the seed
dropped in, and the ridge hoed up. In some districts, however, this
custom is varied by the ridges being made after the sowing. The
water lies in the hollows between the ridges, prevents the seeds
from being washed away by the torrential downpour, and allows air
to circulate freely, thus keeping the plants in a healthy state. A month
later, when the plants have grown to a foot or more, the ground is
again hoed. That is the first sowing. With variations according to
localities there are successive sowings up to July and even August.
The success of these late sowings depends very much upon the
extent to which the land has been previously manured. Conditions
are slightly different with the variety of cotton grown, but as a rule the
plants are in a fit condition for picking about five months after
sowing. December, January, March, and April appear to be the
months when cotton is most abundant in the markets. In November
and December of last year I observed that while in some of the fields
the pods were bursting well and picking beginning, in others they
were still in full flower; in others, again, they had not reached the
flowering stage. Speaking generally, the plantations were in excellent
condition, and the absence of weeds would have done credit to an
up-to-date British farmer. But the difference in vigour of plant growth
was very marked—affected, doubtless, by locality and manuring or
the lack of it. One of the finest plantations I saw was at Gimmi, to the
north of Zaria province, and the intelligent sariki (chief) of that village
informed me that his people not infrequently treated the plant as a
perennial up to the third year, when it was plucked up. I
subsequently ascertained that in the Hadeija division of the Kano
province, where the soil has a good underlying moisture, the
perennial treatment is carried on sometimes for no less than seven
years. After the third year the annual crop decreases. When so
treated the plant is invariably manured.
I found it exceedingly difficult to obtain reliable figures as to the
average yield of cotton per acre in any one district, or the average
acreage under cultivation; and the Residents share the view that
only continuous residence in the country by a Hausa-speaking (that
is essential) European expert in constant and close touch with the
farmers will permit of anything approaching exact information being
acquired on the point. In the Katagum division of Kano province an
acre is said to produce an average of 266 lbs. The average annual
acreage under cotton in Katsina is said to be 16,000 acres. In Zaria
province the soil, which is a sandy clay, the subsoil being reached at
six inches, is generally rather poor, and the farmer is not so great an
expert as his Kano colleague. In some places it is so poor that one
hundred plants are said to be required to produce a single riga. In
the true cotton-farming districts of the northern part of the province—
such as Soba, Gimba, and Dillaya—the soil is, however, very much
better, obtaining more moisture than the higher ground of Kano
province and producing even finer cotton. Broadly, the problem
which faces the native farmer in Zaria province is how to increase
the fertility of his land. Artificial chemical manuring is out of the
question; the rains would wash it all out of the soil. Green manuring
is well understood but might be improved. The introduction of one or
two shallow ploughs might work wonders by showing the farmers
how the subsoil could be broken up, but the experiment would have
to be carefully demonstrated. The native is only affected by actual
demonstration, and, so far, demonstrations inspired by Europeans
designed to show the Hausa farmer how to improve his agricultural
systems have done little more than provoke a smile. The white man
has failed where the black man has succeeded, because the white
man thought he knew local conditions and did not. A Government
experimental farm was started at Maiganna rather late last year, the
sowings being made in July, if I remember rightly, seventeen miles
from Zaria city. This is an excellent initiative which it is to be hoped
will be maintained. It is really Government work. The British Cotton-
growing Association should be spared all expense of this kind. Two
varieties indigenous to the southern provinces (Bassa and Ilorin) and
“Nyassaland upland” were planted. I was told last November by the
official in charge that the indigenous varieties were doing fairly well,
but that the “Nyassaland” was suffering from red-leaf. The British
Cotton-growing Association was then about to put up a large and
costly ginnery at Zaria. The operation is proceeding, and a
substantial quantity of cotton has already been bought. I will refer to
that later on. Meantime I cannot help thinking that it might have been
better to have waited a little and set up the ginnery at Kano.
However, this is merely a personal opinion.
The chief varieties of indigenous cotton grown in the Kano
province are three in number. The first is known under the four
following names—gundi, bagwandara, lutua, or mailaushi; the
second as chukwi or labai. These two are the best kinds, their quality
being about the same. The third is called yerkarifi or yergeri. It is of
an inferior quality with a shorter staple, usually but not always grown
where the soil is not naturally rich enough to support the other kinds.
It is the yerkarifi variety, I gathered, which is more often used as a
perennial. It fetches a lower price on the local markets and takes a
month longer to mature. Cotton plants are fairly free from insect
pests, but the following are identified: the cotton boll worm (tsutsa),
what is described, doubtfully, as an ant which attacks the root (zago),
and two species of blight (makau and madi). The native remedy,
apart from constant hoeing, is to light a fire to windward, upon which
the dried leaves of a certain plant, and also dried fish, are thrown.
The question of indigenous versus exotic varieties here crops up
again. One hears talk of flooding the country with exotic seed and
doing away altogether with the indigenous varieties. I refer to Zaria,
where some five hundred bags of exotic seed—or at least non-local
seed—were distributed this spring after a palaver with the Emir and
his principal headmen. No doubt it may be all right. From the non-
expert point of view it seems dangerous. As already stated, African
insect life fastens with relentless savagery upon exotic plant life, just
as it revels in nice fresh blood out from Europe. One season’s failure
with an exotic or non-local variety, sown by instructions of the Emir’s
headmen in lieu of the indigenous kind, might create a prejudice in
the native’s mind that it would take years to remove. Concentration
upon improving the fertility of the soil, and therefore the quality and
quantity of the local varieties (combined, of course, with seed
selection) would be a slower process. It is just possible that it might
be a wiser one.
The distribution of the cotton now grown in Zaria and Kano
provinces is as follows: Zaria is visited by the weavers (or their
representatives) of Kano and of French territory—from the
neighbourhood of Zinder principally. They buy up between them
virtually the whole crop, importing live stock and manufactured
goods, which they dispose of in the markets for silver coin, buying
with that coin the cotton. What is not taken by the Zinder people is
taken by Kano. The Kano division of the Kano province consumes all
the cotton it grows. So does the Katagum division. The Katsina
division exports a percentage to Kano and consumes the rest. The
soil of this division compares unfavourably with that of Kano, except
in the southern district, where it is even better than in Kano. In this
district cotton-growing forms the principal means of livelihood of the
inhabitants. The total annual output of the Kano province is
estimated at about 5200 tons—3500 from the Kano division, 1000
from the Katsina division, 700 from Katagum-Hadeija. But these
figures are mere estimates, and not over-reliable at that. The country
is too extensive and the British occupation too recent to permit of
accuracy in such matters at present. I was unable to obtain even an
estimate of the Zaria output, which is, of course, very much lower—
probably about one-fifth, or less than that at Kano.
As already remarked, the whole of the crop now grown is used by
the local industry (except the Association’s purchases this year,
which I will refer to in a moment). So far this industry not only shows
no signs of decreasing, but the demand, especially from the
southern markets is, I was told, steadily increasing. The advent of
the railway may, apart from the activities of the Association, modify
the situation appreciably through the increasing influx of Manchester
goods. As well-being increases—and up to a certain point it is doing
and will do so as the result of our occupation—the consumption of
Manchester goods wall doubtless increase, but it does not altogether
follow that the output of the native looms will decrease. It is curious
that the Kano weavers themselves think that the railway will enlarge
their market. I was informed that the natives of the south, who have
been in touch with Manchester cotton goods for many years, very
much prefer the Kano cloths, which although dearer, are much more
durable. In the north I heard frequent complaints of the quality of the
Manchester goods imported. Many of them, so I was told, were
much too thin, and so heavily starched that on the first washing they
became threadbare and useless. I saw nothing on sale in the
markets from Manchester suited for the early and late hours of the
day. Cheap prints are all very well for the hot hours of the late
morning and afternoon. But the people require warmer garments
than that. I used to strike camp when trekking at about 5 a.m. or 5.30
a.m., and at that time, and for a couple of hours afterwards, I was
glad of two sweaters over a khaki shirt, riding. When the sun goes
down it is equally chilly. The robes worn by the better-class natives
are of a consistency and weight which would astonish us here.
 I am persuaded that the British Cotton-growing Association is in
every way worthy of support, that its ideal is a fine one and a
patriotic one, and that the West African dependencies of Southern
and Northern Nigeria are very much indebted to it. At the same time I
should not be giving honest expression to the views I have rightly or
wrongly formed if I did not enter a caveat against any Government
action calculated to undermine or destroy the weaving industry of the
Kano province. That industry may disappear as the result of natural
causes. But nothing should be done by the Administration to assist
its decay. Frankly, I am compelled to state that from the standpoint of
the happiness and welfare of these Hausa people, our wards, the
disappearance of their national industry would be deplorable. It
would lower their outlook and stunt their development, and send
them down in the scale of civilization. Their intelligence is of an order
which would enable them under tuition to advance their methods of
production beyond the hand-loom. While the duty of the
Administration to lend its moral support, as it is doing, from the
Governor, Sir Henry Hesketh Bell (who is most interested in this
question) downwards, to any legitimate effort directed at increasing
the area of cotton under cultivation, increasing the yield per acre by
improving the fertility of the soil, facilitating communication and the
accessibility of markets, is unquestioned, I submit that there is an
equally clear call of duty on its part to encourage rather than
discourage an indigenous industry of great antiquity, of wonderful
promise, which is at once a source of profit to, and an elevating
influence in, the life of the people of the land.
I have now endeavoured to sketch the chief factors to be
considered in estimating the possibilities of a substantial export trade
in raw cotton from Northern Nigeria. There remains to be examined
the question of price and of competing articles of production. The
British Cotton-growers Association’s début at Zaria has been
attended with no little success. They bought this season, I believe,
something like 60,000 lbs. of cotton, a considerable proportion of
which, I am informed, came from the Katsina division of Kano. Whilst
the Association’s buyers, lent to its representative by the authorities,
could not compete in price with the Kano and Zinder buyers in the
big markets, they competed successfully with them in the remoter
small markets of the province which buyers from the native weaving
interest do not usually visit.
I hope I shall not be thought desirous of “crabbing” the
Association’s efforts or minimising what they have accomplished if I
venture to point out that there would be some danger—of which the
Association is doubtless aware—in drawing too definite conclusions
from these first and satisfactory results. The taxes fell due in Zaria
province at the time of the maturing of the crop, and the growers
were anxious for cash to meet them. The Emir of Katsina is a very
intelligent man and wishful of encouraging in every way he can any
desires he deems the Government to entertain. His influence would
be directed to giving a tangible proof of his interest and goodwill.
This desire would be shared by his people, by whom he is personally
respected. It would be unwise, however, to imagine that Katsina
farmers will permanently be willing to send their cotton all the way to
Zaria for 1d. per lb., when in the ordinary run of things they can get
as much, if not more, than 1d. from the native weaving interest. If the
cotton were bought on the spot the farmers might be willing to sell at
1d. The question of price is bound to play an important part in the
interesting developments which have now begun. Taking year in year
out, the local price of cotton in Zaria and Kano varies from 1¼d. to
2d. per lb. in the seed. In Zaria last November and December it
varied from 1⅝d. to 2d. In Kano it kept at 2d. throughout November,
December, and part of January, having fallen from 2¼d. in
September. In the latter part of January it fell temporarily to 1d. It
went up again to 2d. in February. The bright side consists in the
possibility—the probability, perhaps—that the knowledge of a
permanent and unlimited market at a fixed price, albeit a low one, in
their midst will incline farmers to patronize that market (and increase
their acreage), assuring them as it does of an immediate sale.
Personally, I cannot but think that the Association will have to put up
its price if it is to obtain substantial quantities. Competition here, as
in Southern Nigeria, would undoubtedly tend to increase production,
but I believe that the advent of the European merchant to Zaria and
Kano is to be characterized by the same arrangement as I have
already commented upon in Southern Nigeria. There is, of course,
what there is not in Southern Nigeria, an element of competition in
the Northern provinces—viz. the native weaving interest—and the
play of these two forces, if both are allowed a fair field, will, no doubt,
have a stimulating effect in itself.
Another element comes in here which is worthy of note. I refer to
the price of foodstuffs. Everywhere the price of foodstuffs is growing
with our occupation of the country. Round the main highways and
large markets it has risen enormously in the past eighteen months.
In one part of the Niger province the native farmer now reckons upon
getting, I was informed, £8 to £10 per acre out of yams. Cotton at 1d.
per lb. would bring him in from £3 to £4. That is rather an extreme
case, I admit, nor does the whole country produce yams, and the
farmers generally do not appear yet to have fully grasped the
economic importance for them of the increased demand for
foodstuffs. On the other hand, it is, of course, true that the sowing of
cotton between the ordinary food crops is not uncommon.
I have thought it well to describe the position just as I read it, and
to make certain suggestions, the outcome of personal observation
and discussion on the spot. It may well be that in certain respects I
have read the situation wrong and that the suggestions made are
faulty. Prediction at the present time, I am convinced, must be largely
made in the dark, and they are no friends of the British Cotton-
growing Association who describe the outlook in Nigeria in “high
falutin’” terms. It is too soon to say how matters will develop. That
development will in any case be slow may be taken for granted. The
Administration is in urgent need of a properly equipped agricultural
department with at the head of it the very best man that money can
secure.
Reviewing the whole situation, the only definite conclusions I have
been able to arrive at in my own mind are—first, that all attempts at
giving an artificial basis to cotton production in the Nigerias will, in
the long run, defeat its own ends; secondly, that by some means or
other the price paid to the native farmer must be raised if any
extension of the industry worth talking about is to be looked for.
Everywhere in Northern Nigeria, whether the personal view inclines
to optimism or pessimism, I found the officials without exception
deeply interested in and anxious to assist in every way the effort to
build up an export industry in cotton, and fully persuaded of the great
importance and value of the work of the Association.
 CHAPTER IV
THE LIQUOR TRAFFIC IN SOUTHERN NIGERIA

Apart from religious questions there is probably no subject upon

which it is more difficult to secure reasonable discussion and study
than the subject of drink; none upon which it is more easy to
generalize, or which lends itself more readily to prejudice and
misunderstanding of the real points at issue. That moral reformers in
England and elsewhere should feel strongly about drink is natural
enough. A considerable proportion of the population of this country,
of France, Germany, Belgium, and other European States live
wretched and unhealthy lives. They are over-worked, under-fed,
herded in insanitary tenements with insufficient space, ventilation,
and light, under conditions which preclude decency and breed moral
and physical diseases. Their horizon is one dead, uniform, appalling
greyness from birth to death. Who can feel surprise that people thus
situated should seek momentary forgetfulness in drink? The drink
problem in Europe is not a cause but an effect. The cause lies deep
down in the failure-side of our civilization, and statesmen worthy of
the name are grappling with it everywhere. Those of us who think we
see beyond an effect, are striving to prevent the reproduction in
tropical Africa of this failure-side of our civilization. We are striving to
maintain the economic independence of the West African; to ensure
him a permanency of free access to his land; to preserve his healthy,
open-air life of agriculturist and trader, his national institutions, his
racial characteristics and his freedom. We are endeavouring to show
him to the people of Europe, not as they have been taught by long
years of unconscious misrepresentation to regard him, but as he
really is. We feel that if we can protect the West African from the
profounder economic and social perils which encompass him on
every side; from the restless individualism of Europe; from unfair
economic pressure threatening his free and gradual development on
his own lines; from the disintegrating social effects of well-meaning
but often wrongly informed and misdirected philanthropic effort; from
political injustice—that if we are able to accomplish this even in small
measure, the question of drink, while requiring attention, becomes
one of secondary importance. The West African has always been a
moderate drinker. From time immemorial he has drunk fermented
liquors made from various kinds of corn, and from different kinds of
palm trees. It is not a teetotal race, as the North American race was.
It is a strong, virile race, very prolific.
Unfortunately this question of drink has been given a place in the
public mind as regards Southern Nigeria altogether disproportionate
to the position it does, and should, hold. It has been erected for
many sincere, good people into a sort of fetish, obscuring all the
deeper issues arising from the impact upon the West African of
civilization at a time when civilization has never been so feverishly
active, so potent to originate vast changes in a few short years. The
temperance reformer in England strikes, often blindly, at “drink”
anywhere and everywhere on the same principle, utterly oblivious to
physiological and climatic differences; he cannot see beyond or
behind the subject which specially interests him and which has
become his creed. The use of intoxicants of some kind is common to
humanity all over the world. It responds to a need of the human
body. Christ Himself did not condemn its use, since He Himself, the
Sacred Writings tell us, changed water into wine at a marriage feast.
Excessive indulgence in liquor, like indulgence in any other form of
human appetite, is a human failing. It is not the drink which is an evil,
but the abuse of it. The abuse of liquor nine times out of ten is the
outcome of social discomfort and unhappiness, a way of escape, like
a narcotic, from the pangs of conscience, or of misery. People who
concentrate merely upon effects are unsound guides when
constructive measures are required. The temperance reformer in
England approaches the question of drink in West Africa from the
subjective point of view which characterizes the home outlook upon
most questions lying outside the home latitudes. Saturated with his
home experience, the English temperance reformer places the West
African in the same economic and social setting as the European
and argues on parallel lines. To that mode of reasoning, three-
fourths of the evils which civilization has inflicted upon coloured
races may be traced. Nothing is more curious or more saddening to
observe than the unfailing success of such methods of thought
translated into public action, in their effect upon home sentiment.
Consumption sweeping through the ranks of a coloured people as
the consequence of the educationary and religious processes of
Europeanism may make a holocaust of human victims. The public
remains indifferent. European marriage laws; European ethics, or
nominal ethics, in the matter of sex relationship; the European
individualistic social system grafted upon the communal life of a
coloured people—these things may produce widespread human
misery and immorality. The public is cold and unconcerned.
European interference and innovation in social customs and usages
essential to the well being, to the political and racial needs of a
coloured people in one stage of development, but repugnant to
European twentieth-century notions, may cause social disturbance
and widespread anarchy which those who are responsible for such
interference can never themselves witness, let alone suffer from. It is
virtually impossible to arouse popular interest. For these and kindred
disasters are very largely brought about by the uninstructed zeal of
God-fearing, Christian men and women in Europe who judge other
countries by their own, other peoples by their own people, other
needs by their own needs, with the best of intentions and with the
purest of motives; and outside a small band of students, ethnologists
and experienced officials, the public mind is scandalized and even
incensed if any one ventures to doubt the excellent results
necessarily flowing from disinterested action. It is disinterested:
therefore it must be right. That is the popular belief and the general
fallacy.
Poor Mary Kingsley, who knew her West Africa as few have ever
known it and who had the true scientific mind, fought hard against
this ingrained characteristic of the Anglo-Saxon temperament. But
she fought in vain. Despite her charity, the geniality and the humour
in which she clothed her truths, she had against her the whole
weight of what is called the philanthropic school of home opinion,
responsible for so much good and yet for so much unconscious
harm.