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Electronic Noses and Tongues in Food

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Electronic Noses and
Tongues in Food Science

Series Editor
Victor Preedy
Department of Nutrition and Dietetics,
King’s College London,
United Kingdom

Editor
María Luz Rodríguez Méndez
Group of Sensors
Industrial Engineering School
University of Valladolid, Spain

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Contributors

Numbers in paraentheses indicate the pages on which the authors’ Carla Guanais Branchini (301), Department of Chemi-
contrbutions begin. cal Science and Technologies, University of Rome “Tor
A.H. Abdullah (103), Centre of Excellence for Advanced Vergata,” Rome, Italy
Sensor Technology (CEASTech), Universiti Malaysia Jesús Brezmes (49), SIPOMICS, Department of Elec-
Perlis, Perlis, Malaysia tronic Engineering, Universitat Rovira i Virgili, Avda.,
Priscila Alessio (171), Faculty of Science and Technology, ­Tarragona, Spain
Sao Paulo State University (UNESP), São Paulo, Brazil Susanna Buratti (291), Department of Food, Environmen-
Jayendra Amamcharla (59), Animal Sciences & Industry, tal and Nutritional Science, University of Milan, Milan,
Kansas State University, Manhattan, KS, United States Italy
of America Xavier Cetó (235), Sensors and Biosensors Group, Depart-
Francesca Antonucci (73), Consiglio per la ricerca in ment of Chemistry, Autonomous University of B­ arcelona,
­agricoltura e l’analisi dell’economia agraria (CREA), Barcelona, Spain; Mawson Institute, University of South
Agricultural engineering research unit, Rome, Italy Australia, Mawson Lakes, SA, Australia

Constantin Apetrei (277), Department of Chemistry, Patrycja Ciosek (209), Department of Microbioanalytics,
Physics and Environment, Faculty of Sciences and Envi- Faculty of Chemistry, Warsaw University of Technol-
ronment, “Dunarea de Jos” University of Galati, Galati, ogy, Warsaw, Poland
Romania Salvatore Claps (73), Consiglio per la ricerca in agri-
Sundar Balasubramanian (59), PepsiCo America Bever- coltura e l’analisi dell’economia agraria (CREA),
ages R&D, Barrington, IL, United States of America Research Unit for the Extensive Animal Husbandry,
Bella, Italy
Ulrich Banach (115), Bundesanstalt für Materialforschung
und –prüfung (BAM), Berlin, Germany Carlos José Leopoldo Constantino (171), Faculty of
Science and Technology, Sao Paulo State University
Rajib Bandyopadhyay (125, 245), Department of Instru- (UNESP), São Paulo, Brazil
mentation and Electronics Engineering, Jadavpur Uni-
versity, Kolkata, India Maria Stella Cosio (83), Department of Food, Environ-
mental and Nutritional Sciences, University of Milan,
Runu Banerjee(Roy) (125), Department of Instrumenta- Milano, Italy
tion and Electronics Engineering, Jadavpur University,
Kolkata, India Corrado Costa (73), Consiglio per la ricerca in agricoltura
e l’analisi dell’economia agraria (CREA), Agricultural
José M. Barat (199), Departamento de Tecnología de los engineering research unit, Rome, Italy
Alimentos, Universitat Politècnica de València, Spain
Cristiane Margarete Daikuzono (171), São Carlos Institute
Nadia Bazihizina (73), Production Sciences Department of of Physics, University of São Paulo, São Paulo, Brazil
Agri-Food and the Environment, University of ­Florence,
Sesto Fiorentino, Italy Osvaldo Novais de Oliveira, Jr (171), São Carlos Insti-
tute of Physics, University of São Paulo, São Paulo,
Simona Benedetti (291), Department of Food, Environ- Brazil
mental and Nutritional Science, University of Milan,
Milan, Italy José A. De Saja (265), Group of Sensors, Industrial Engi-
neering School, University of Valladolid, Spain
Nabarun Bhattacharyya (125, 245), Centre for Develop-
ment of Advanced Computing, Kolkata, India Manel del Valle (235), Sensors and Biosensors Group,
Department of Chemistry, Autonomous University of
Evandro Bona (31), Federal University of Technology— ­Barcelona, Barcelona, Spain
Paraná (UTFPR), Campo Mourão, Paraná, Brazil

xi
xii Contributors

Corrado Di Natale (301), Department of Electronic Eduard Llobet (49), MINOS-EMaS, Department of Elec-
Engineering, University of Rome “Tor Vergata,” Rome, tronic Engineering, Universitat Rovira i Virgili, Avda,
Italy Tarragona, Spain
Luís G. Dias (179), Agrarian School, Polytechnic Institute of Jesús Lozano (137), GRIDSEN, Institute of Physics
Bragança, Campus Santa Apolónia, Bragança; ­CQ-VR, and Technology Information, Superior Council for
Chemical Center–Vila Real, University of Trás-os- Scientific Research, Madrid; University of Extremad-
Montes e Alto Douro, Vila Real, Portugal ura, School of Industrial Engineering, Badajoz, Spain
Rui Sérgio dos Santos Ferreira da Silva (31), State Uni- Larisa Lvova (151, 301), Department of Chemical Science
versity of Londrina (UEL), Londrina, Paraná, Brazil and Technologies, University of Rome Tor Vergata,
Mats Eriksson (255), Department of Physics, Chemistry Rome, Italy; Institute of Earth Sciences, Saint-Petersburg
and Biology, Linköping University, Linköping, Sweden State University, Saint-Petersburg, Russia
C. García-Hernández (265), Group of Sensors, Industrial Stefano Mancuso (73), Production Sciences Department
Engineering School, University of Valladolid, Spain of Agri-Food and the Environment, University of Flor-
ence, Sesto Fiorentino, Italy
Eduardo Garcia-Breijo (199), Centro de Reconocimiento
Molecular y Desarrollo Tecnológico (IDM), Universitat Ramón Martínez-Máñez (199), Centro de R ­ econocimiento
Politècnica de València, Valencia, Spain Molecular y Desarrollo Tecnológico (IDM), Universitat
Politècnica de València, Valencia; CIBER de Bioing-
Mahdi Ghasemi-Varnamkhasti (277), Department of eniería, Biomateriales y Nanomedicina (CIBER-BBN),
Mechanical Engineering of Biosystems, Shahrekord
­ Spain
University, Shahrekord, Iran
M.J. Masnan (103), Institute of Engineering Mathematics,
Arunangshu Ghosh (245), Department of Instrumenta- Pauh Putra Main Campus, Universiti Malaysia Perlis,
tion and Electronics Engineering, Jadavpur University, Perlis, Malaysia
­Kolkata, India
C. Medina-Plaza (265), Group of Sensors, Industrial Engi-
Luis Gil-Sánchez (199), Centro de Reconocimiento Mo- neering School, University of Valladolid, Spain
lecular y Desarrollo Tecnológico (IDM), Universitat
Politècnica de València, Valencia, Spain Paolo Menesatti (73), Consiglio per la ricerca in agricol-
tura e l’analisi dell’economia agraria (CREA), Agricul-
M.T.S.R. Gomes (21), CESAM & Department of Chemis- tural engineering research unit, Rome, Italy
try, University of Aveiro, Aveiro, Portugal
Irina Mirela Apetrei (277), Department of Pharmaceutical
Manuel Gutiérrez-Capitán (189), Instituto de Micro- Sciences, Faculty of Medicine and Pharmacy, “Dunarea
electrónica de Barcelona (IMB-CNM), CSIC, Campus de Jos” University of Galati, Romania
UAB, Bellaterra, Spain
Giuseppe Morone (73), Consiglio per la ricerca in
Thomas Hübert (115), Bundesanstalt für Materialforsc- ­agricoltura e l’analisi dell’economia agraria (CREA),
hung und –prüfung (BAM), Berlin, Germany Research Unit for the Extensive Animal Husbandry,
M. Carmen Horrillo (137), GRIDSEN, Institute of Phys- Bella, Italy
ics and Technology Information, Superior Council for O. Omar (103), Malaysian Agricultural Research and
Scientific Research, Madrid, Spain ­Development Institute (MARDI), Penang, Malaysia
Guohua Hui (15), School of Information Engineering, Federico Pallottino (73), Consiglio per la ricerca in agri-
Key Laboratory of Forestry Intelligent Monitoring and coltura e l’analisi dell’economia agraria (CREA), Agri-
­Information Technology of Zhejiang Province, ­Zhejiang cultural engineering research unit, Rome, Italy
A & F University, Linan, China
Roberto Paolesse (301), Department of Chemical Science
Cecilia Jiménez-Jorquera (189), Instituto de Microelec- and Technologies, University of Rome “Tor Vergata,”
trónica de Barcelona (IMB-CNM), CSIC, Campus UAB, Rome, Italy
Bellaterra, Spain
António M. Peres (179), Laboratory of Separation and Re-
Dmitry Kirsanov (225), Chemistry Department, St. Peters- action Engineering–Associate Laboratory, LSRE-LCM,
burg State University, St. Petersburg, Russia Agrarian School, Polytechnic Institute of Bragança,
Aleksander Kubiak (93), Department of Food Science and Campus Santa Apolónia, Bragança, Portugal
Department of Process Engineering and Equipment, Uni- Krishna Persaud (3), School of Chemical Engineering
versity of Warmia and Mazury in Olsztyn, Olsztyn, Poland and Analytical Science, The University of Manchester,
Andrey Legin (225), Chemistry Department, St. Peters- Manchester, United Kingdom
burg State University, St. Petersburg, Russia
Contributors xiii

N.A. Rahim (103), Centre of Excellence for Advanced Jin-E Shin (59), PepsiCo America Beverages R&D,
Sensor Technology (CEASTech), Universiti Malaysia ­Barrington, IL, United States of America
Perlis, Perlis, Malaysia Maria Concetta Strano (73), Consiglio per la ricerca in
Antonio Riul, Jr (171), Institute of Physics “Gleb Wataghin,” agricoltura e l’analisi dell’economia agraria (CREA),
University of Campinas (UNICAMP), SP, Brazil Research center for citrus and Mediterranean crops,
María Luz Rodríguez Méndez (265), Group of Sensors, Acireale, Italy
­Industrial Engineering School, University of Valladolid, Yusuke Tahara (161), Graduate School of Information
Spain Science and Electrical Engineering, Kyushu University,
Lígia R. Rodrigues (179), CEB—Centre of Biological Fukuoka, Japan
Engineering, University of Minho, Campus de Gualtar, Cosimo Taiti (73), Production Sciences Department of
Braga, Portugal ­Agri-Food and the Environment, University of ­Florence,
María Teresa Rodriguez-Estrada (39), Interdepartmen- Sesto Fiorentino, Italy
tal Centre for Agri-food Industrial Research, Univer- Pradip Tamuly (245), Tea Research Association, Jorhat,
sity of Bologna; Department of Agricultural and Food Assam, India
­Sciences, University of Bologna, Bologna, Italy Carlo Tiebe (115), Bundesanstalt für Materialforschung
Santina Romani (39), Interdepartmental Centre for Agri- und –prüfung (BAM), Berlin, Germany
food Industrial Research, University of Bologna; Depart- Kiyoshi Toko (161), Graduate School of Information Sci-
ment of Agricultural and Food Sciences, University of ence and Electrical Engineering, Kyushu ­University,
Bologna, Bologna, Italy Fukuoka; Research and Development Center for Taste
Andrea Romano (83), Free University of Bolzano, Faculty and Odor Sensing, Kyushu University, F ­ukuoka,
of Science and Technology, Bolzano, Italy ­Japan
Alisa Rudnitskaya (225), CESAM and Chemistry Depart- Bipan Tudu (125, 245), Department of Instrumentation and
ment, Aveiro University, Aveiro, Portugal Electronics Engineering, Jadavpur University, K
­ olkata,
F.S.A. Sa’ad (103), Centre of Excellence for Advanced India
Sensor Technology (CEASTech), Universiti Malaysia Mikhail Yu. Vagin (255), Department of Physics, Chem-
Perlis, Perlis, Malaysia istry and Biology, Linköping University, Linköping,
José Pedro Santos (137), GRIDSEN, Institute of Physics Sweden
and Technology Information, Superior Council for Sci- Ana C.A. Veloso (179), Polytechnic Institute of Coimbra,
entific Research, Madrid, Spain ISEC, DEQB, Coimbra; CEB—Centre of Biological
Matteo Scampicchio (83), Free University of Bolzano, Engineering, University of Minho, Campus de Gualtar,
Faculty of Science and Technology, Bolzano, Italy Braga, ­Portugal
Lucia Sepe (73), Consiglio per la ricerca in agricoltura e Fredrik Winquist (255), Department of Physics, Chem-
l’analisi dell’economia agraria (CREA), Research Unit istry and Biology, Linköping University, Linköping,
for the Extensive Animal Husbandry, Bella, Italy Sweden

A.Y.M. Shakaff (103), Centre of Excellence for Advanced A. Zakaria (103), Centre of Excellence for Advanced
Sensor Technology (CEASTech), Universiti Malaysia Sensor Technology (CEASTech), Universiti Malaysia
Perlis, Perlis, Malaysia Perlis, Perlis, Malaysia
Preface

Electronic noses and tongues are the products of advanced chemical and physical sciences combined with the intuitive in-
tegration of sensors, microprocessors, advanced informatics, and statistics. They include resistive, optical, electrochemical,
or piezoelectrical platforms, where a variety of sensing materials (including, among many others, metal oxide semiconduc-
tors, conducting polymers, nanoparticles, phthalocyanines, or enzymes) have been immobilized using numerous different
techniques.
Some of these devices are available commercially, whereas others are home-grown prototype devices that require
commercialization. Electronic noses and tongues have been used to characterize components that contribute to sensory
or compositional profiles, from ripening to harvesting and from storage of raw materials to packaging and consumption.
Electronic noses and tongues are thus suitable for high-throughput analysis and quality control or for determining the
nature and extent of spoilage and adulteration. These devices have also been used to ascertain the geographical origins of
food and mixtures. Devices used to analyze one particular food item can theoretically be adapted for other food items or
components. This does not just mean redeploying the sensing devices but also the mode of statistical analysis. This includes
supervised and unsupervised tools such as principal component analysis (PCA), linear discriminant analysis (LDA), partial
least squares (PLS), and artificial neural networks (ANN). In other words, there is cross-transference of chemistry, phys-
ics, concepts, techniques, findings, and approaches from one food to another. However, finding all this information in a
coherent and comprehensive text has been a problem because, until now, no publication has attempted to marshal together
all the relevant information on these important devices in relation to food science. This is addressed in “Electronic Noses
and Tongues in Food Science.”
Its unique feature is the three parts dedicated to the electronic nose, the electronic tongue, and the combined systems
of electronic nose and tongue. Part I covers a description of electronic nose systems and their applications to the analysis
of the volatile composition of different foods and beverages. Part II focuses on the electronic tongue, which has become
increasingly important over recent years because it can analyze complex liquids, such as wines or milk, by direct immersion
in the samples and not restricted to the headspace. Part III covers newer developments combining both the electronic nose
and tongue. Each part presents the main applications in the food industry. Not only classical applications in the fields of
meat, wine, dairy products, or beers are presented but also other lesser-known applications, such as the detection of gliadins
or the assessment of the phenolic content in foods.
This book is designed for food scientists, technologists, and food-industry workers, as well as research scientists. Con-
tributions are from leading national and international experts, including those from world-renowned institutions. Readers
can dip into the book for reference purposes, read any chapter as a standalone treatise, or read it from cover to cover if food
analysis is an integral part of their day-to-day job.
I must conclude by thanking all those who have contributed to this book, each a recognized expert in their field. I also
wish to thank Elsevier Publishing for all the guidance on pulling together such an eclectic book. Finally, many thanks to my
colleagues and PhD students for their help and support!

Professor María Luz Rodríguez Méndez

xv
Chapter 1

Electronic Noses and Tongues


in the Food Industry
Krishna Persaud
School of Chemical Engineering and Analytical Science, The University of Manchester,
Manchester, United Kingdom

needs to be augmented with other types of measurements


1.1 INTRODUCTION
for different ions, ionic strength, pH, viscosity, and so on,
The analysis of food flavors is complicated because of that give an overall impression of the food sample.
several factors. The flavor active compounds are found in Despite advances in instrumental analysis, the flavor
very low concentrations, ranging from a few hundred parts sensations perceived by humans can be measured only by
per million for strongly flavored food products to less than sensory tests (Noble, 2006; Simon et al., 2008; Simons and
10 ppm for weakly flavored foods. In development of new Noble, 2003). Three types of sensory testing are common-
products, manufacturing quality control, shelf-life control, ly used, each with a different goal and using participants
monitoring degradation during transportation and moni- selected using different criteria. These primary kinds of
toring of highly perishable foods, such as fish, the use of sensory tests focus on the existence of overall differences
analytical instruments are important. Monitoring of food among products (discrimination tests), specification of at-
products in terms of quality and control of production pro- tributes (descriptive analysis), and measuring consumer
cesses, such as mixing, heating, drying, cooking, baking, likes and dislikes (affective or hedonic testing). Correct ap-
extruding, fermenting, and so forth are normally performed plication of sensory technique involves correct matching of
using physicochemical measurements, that is, pH-value, a method to the objective of the tests, and this requires good
color, concentration of given chemicals or biomolecules communication between sensory specialists and end users
generally determined by spectroscopy [Fourier transform of the test results (Lawless, 2013).
infrared (FTIR), near infrared (NIR), ultraviolet–visible The aroma components of the majority of food products
(UV–Vis), etc.]. This is due to the lack of reliable odor and consist of complex mixtures of chemicals consisting of sev-
taste-assessing instruments and the practical problems asso- eral hundred or thousands of volatile compounds. These,
ciated with using sensory panels for continuous monitoring together with taste components perceived as salty, sour,
of aroma or flavor. Headspace gas chromatography (HGC) sweet, bitter, umami, and others combine to give to a food
and two-dimensional gas chromatography using different its characteristic flavor. Volatiles and flavor compounds
types of detectors, for example, mass spectrometry coupled can originate at every production stage from all food com-
to olfactometry (Wardencki et al., 2009) can give detailed ponents. They are present in the raw materials and they can
chemical composition data as well as the information on be generated during the food processing as well as during
organoleptic qualities of individual volatile compounds food storage (Plutowska and Wardencki, 2007).
present in the mixture (Cordero et al., 2015). These types Important flavor components that contribute to the per-
of analyses can be very useful in developing new products, ceived organoleptic qualities of foods include aldehydes, al-
or for detection of components that may degrade organolep- cohols, ketones, acids, esters, lactones, phenols, terpenoids,
tic quality, but are very time consuming and expensive to sulfur-containing compounds, pyrazines, and amines. Off-
run. While these techniques are useful for analyzing vola- odors and flavors can be generated by bacterial action on
tile components for compounds involved in taste that are food substrates, molds, and fungi, and biochemical reac-
dispersed in aqueous medium, often in complex matrices, tions (enzymatic reactions as well as chemical reactions).
it become much more difficult—high-pressure liquid chro- We generally think about flavor as one of the three main
matography coupled with electro-spray mass spectrometry sensory properties when choosing a particular food; appear-
can give some idea of the chemical composition, but this ance and texture are the other two properties. For humans

Electronic Noses and Tongues in Food Science. http://dx.doi.org/10.1016/B978-0-12-800243-8.00001-9


Copyright © 2016 Elsevier Inc. All rights reserved. 3
4 PART | I The Electronic Nose

the perception of flavor consists of the sensory combina- As such, it attempts to isolate the sensory properties of the
tion and integration of odors, tastes, oral irritation, thermal foods themselves and provides important and useful infor-
sensations, and mouth feel that originate from a particular mation to product developers and food scientists about the
food (Breslin, 2001; Breslin and Spector, 2008). When we sensory characteristics of their products. Sensory evalua-
describe the aroma of foods, we often use the term “taste” tion has been defined as a scientific method used to evoke,
to indicate sensations that usually are quite complex and in- measure, analyze, and interpret those responses to products
clude to a large extent smell sensations. When we introduce as perceived through the senses of sight, smell, touch, taste,
food into our mouth, taste receptors located on the surface and hearing.
of our tongue are stimulated and send signals to the brain.
However, at the same time, especially as a result of mastica-
tion, many volatile components are also released, reaching 1.1.1 Discrimination Tests
the olfactory mucosa through an opening situated on the up- Discrimination tests are used when the sensory specialist
per wall of the palate. This combination of sensations is what wants to determine whether two samples are perceptibil-
makes up “flavor.” The general categorization of flavor can ity different. It is possible for two samples to be chemi-
be the broad sensations perceived when consuming different cally different in formulation, but for human beings not to
foods. From a biological point of view the flavor sensation perceive this difference. Product developers exploit this
can be defined as the perception originated after a substance possibility when they reformulate a product by using dif-
has been taken into the mouth and it is a specific characteristic ferent ingredients while simultaneously not wanting the
of the substance being perceived (Labows and Cagan, 1993; consumer to detect a difference. If the difference between
Lawless, 1991). The multisensory integration that makes up the samples is very large and thus obvious, discrimina-
our perception of flavor is extremely complex and continues tion tests are not useful. Therefore, discrimination testing
to be a fascinating field of study for psychologists and biolo- is most useful when the differences between the samples
gists (Auvray and Spence, 2008; Spence, 2015). are slight. Discrimination tests are usually performed when
The two main sense organs by which flavor is perceived there are only two samples. There are a number of different
are the nose and the mouth. Flavor comes from three differ- tests available, including triangle tests, n-alternative forced
ent sensations: taste, trigeminal (those sensations perceived choice tests, tetrad tests, and polygonal and polyhedral tests
by a human as astringency, pungency, and cooling) sensa- (O’Mahony, 2013).
tions, and aroma. Trigeminal and taste sensations are real-
ized with the presence of food in the mouth. The aroma
sensation occurs when the molecules of the aromatic com- 1.1.2 Descriptive Analysis
pound are detected at the olfactory receptors reaching this Descriptive sensory analysis is a highly sophisticated tech-
site by the nasal or oral passageways. Assessing food quality nique that allows the sensory scientists to obtain complete
is complex, because this translates to assessing appearance, sensory descriptions of products. They help identifying un-
color, organoleptic qualities, and for taste—mouth feel and derlying ingredient and process variables, and/or determine
so forth that results in determining “liking” or “disliking.” which sensory attributes are important to acceptance. Usu-
This assessment is subjective, requiring human noses ally, descriptive techniques produce objective descriptions
and tongues; typically a trained human panel is required. of products in terms of the perceived sensory attributes. De-
The many different possible flavors are due to interactions pending on the specific technique used, the description can
of chemical compounds with taste, trigeminal sensations, be more or less objective, as well as qualitative or quantita-
or aroma receptors. The characteristic taste of a food is nor- tive. Most descriptive methods can be used to define sen-
mally related to a single class of compounds. But, an odor sory instrumental relationships.
is usually elicited by a combination of volatile compounds,
each of which imparts its own smells. Differences in char-
1.1.3 Flavor Profile
acteristics of certain aromas can be equated to the varying
proportions of these volatiles. However, some substances Flavor profiling is a consensus technique. The vocabulary
contain trace amounts of a few volatile compounds that pos- used to describe the product and the product evaluation itself
sess the characteristic essence of the odor. These are called is achieved by reaching agreement among the panel mem-
character-impact compounds. One must also realize that the bers. The flavor profile considers the overall flavor and the
chemicals of a single compound class can induce many di- flavor noted and estimates intensity and amplitude (overall
verse flavors, especially as their concentrations vary. impression) of these descriptors. The technique provides a
Sensory evaluation comprises a set of techniques for tabulation of the perceived flavors, their intensities, their
accurate measurement of human responses to foods and order of perception, their aftertastes, and their amplitude.
minimizes the potentially biasing effects of brand identity If the panelists are trained appropriately, this tabulation is
and other information influences on consumer perception. reproducible. Using standardized techniques of preparation,
Electronic Noses and Tongues in the Food Industry Chapter | 1 5

presentation, and evaluation, a panel consisting of four to combinatorial approach utilizing arrays of broad specificity
six judges are trained to precisely define flavors of a product sensors outlined by Persaud and Dodd (1982) have formed
within a specific food category. The food samples are tast- the basis of many types of “electronic noses” and “electron-
ed and all perceived notes are recorded for aroma, flavor, ic tongues” developed since then. The concepts are based
mouthfeel, and aftertaste. After this exposure, the panelists broadly on our understanding of biological odor and taste
review and refine the descriptors used. transduction mechanisms where large numbers of different
At the completion of the training phase, the panelists odor receptor types or taste receptors respond to the same
have defined a frame of reference for expressing the inten- chemical stimulus but with different affinities. The result
sities of the descriptors used. The samples are then served is a complex pattern of neural responses that the brain as-
to the panelists in the same form that they would be served sociates with previously learned stimuli in order to identify
to the consumer and the intensities of the perceived flavor or discriminate between these chemical stimuli. In order to
notes are rated typically on a defined scale. A consensus understand these concepts, it is worth spending some time
of scores is obtained by discussion and reevaluation of the understanding some of these biological mechanisms.
products by the panelists.
It can be seen that sensory evaluation of foods is very 1.2.1 Biology of Smell and Taste
complex and subject to high variability, and instrumental
means of carrying out some of these evaluations would be The nose is capable of detecting a large repertoire of mol-
most useful to the food industry. The remarkable capabili- ecules—the latest estimates indicate that these may num-
ties of the nose and tongue in detection, recognition, and ber over 1 trillion odors (Bushdid et al., 2014). It resembles
discrimination of complex mixtures of chemicals, together somewhat the concepts inherent in the immune system where
with rapid advances in understanding how these systems it is not possible predict what molecules may be encountered
operate has stimulated the imagination and interest of many at any time. These molecular families include aliphatic and
researchers and commercial organizations for the develop- aromatic molecules with varied carbon backbones and di-
ment of electronic analogues of the biological systems. This verse functional groups, including aldehydes, esters, ketones,
chapter focuses on “electronic noses and tongues” as ap- alcohols, alkenes, carboxylic acids, amines, imines, thiols,
plied to the food industry. The responses of individual odor halides, nitriles, sulfides, and ethers. With rapid advances
sensors or taste sensors combined into an array, by which in molecular biology, we now have a good understanding of
each sensor possesses slightly different response selectivity the transduction processes in the nose and signal-processing
and sensitivity toward the sample odors or tastants, when pathways in the brain that are responsible for detection, dis-
combined by suitable mathematical methods, can provide crimination, and recognition of odors (Firestein, 2001).
information to discriminate between many sample odors About 6 to 10 million olfactory sensory neurons (OSN)
or tastants and when combined together—flavors. Arrays are found in the nasal cavity of mammals. Each of these cells
of gas and odor sensors, made using different technologies is a bipolar neuron where the apical end ends in a knob from
have become known as “electronic noses” and consist of which protrude a number of cilia that lie in a thin layer of
three elements: a sensor array which is exposed to the vola- mucus on the surface of the olfactory epithelium (Fig. 1.1).
tiles; conversion of the sensor signals to a readable format; These cilia contain the sensory transduction mechanisms
and software analysis of the data to produce characteristic constituting receptor proteins and an enzymatic cascade
outputs related to the odor encountered. The output from that transforms the energy of an odorant molecule binding
the sensor array may be interpreted via a variety of meth- to the receptor into a neural signal. There is great degree of
ods—principal component analysis, discriminant function similarity between receptors, but there is a region of hyper-
analysis, cluster analysis, and artificial neural networks—to variability that is associated with the ligand-binding pock-
enable discrimination between samples. A similar approach ets of these proteins. This accounts for the large and diverse
is adopted with “electronic tongues,” by which the sensors range of molecules that can be detected by these receptors
in this case detect chemical species in solution. (Firestein, 2001; Mombaerts, 1996, 1999).
The opening of ion channels in the cell membranes when
an odorant molecule interacts with the receptors causes a
1.2 BIOMIMETIC SYSTEMS change in electrical potential in the cell membrane (Chiu
Attempts to mimic the “chemical senses” using artificial et al., 1997), leading to generation of action potentials that
systems are still in the process of development and have are propagated to the olfactory bulb, a structure in the fore-
been evolving over the last few decades. One of the pio- brain devoted to the processing of olfactory signals. De-
neers in thinking about the concepts, Dravnieks (1968) spite the huge number of olfactory neurons, there are only
envisaged an instrument that would inspect samples of 300–400 different types of receptors in humans. Olfactory
odorous air and report the intensity and quality of an odor neurons expressing a particular receptor type converge to
without the intervention of a human nose. The ideas of a distinct regions in the olfactory bulb called glomeruli. The
6 PART | I The Electronic Nose

FIGURE 1.1 The olfactory epithelium consists of OSNs, which are bipolar neurons, sustentacular cells that are glial cells with microvilli, and
basal cells that are stem cells, from which new OSNs are generated. Each OSN expresses only one of the ∼1000 olfactory receptor genes and the
axons from all cells expressing that particular receptor converge onto one or a few glomeruli in the olfactory bulb. The glomeruli contain the incoming
axons of OSNs and the apical dendrites of mitral cells that are the output layer of cells. Mitral axons leaving the OB project to higher brain structures
including the piriform cortex, hippocampus, and amygdala.

outputs from this region are specialized cells called mitral uncovered (Kinnamon, 2012; Simon et al., 2008; Teeter and
(M/T) cells that propagate a highly reduced number of sig- Brand, 1987). On the tongue are found structures called pa-
nals to higher parts of the brain—many thousand olfactory pillae that contain taste buds (Fig. 1.2). These papillae have
neurons converge onto the dendrites of between 5 and 25 different shapes: fungiform found mainly on the anterior of
mitral cells in each glomerulus. Each ORN type projects into the tongue, foliate along the sides, and circumvallate at the
one or two glomeruli and a single M/T cell receives input back of the tongue. Within each taste bud are found approx-
from just one type of ORN, expressing the same type of re- imately 50–100 cells that contain the transduction elements
ceptor, and sends its axon to the olfactory cortex. Therefore, associated with taste. Taste receptor cells are not neurons,
the first representation of the odor is transduced at the glo- but interrelate with projection neurons that make up the
merular level, to produce a second spatial and very ordered taste nerves. In mammals, the taste buds, depending upon
pattern, representing its molecular features and distributed their location, are innervated by one of several paired crani-
among a much smaller number of output cells (chemotopic al nerves: the chorda tympani (anterior tongue) and greater
coding) (Mombaerts, 1999, 2006; Mori et al., 2006; Mori superficial petrosal (soft palate) branches of the facial nerve
and Sakano, 2011). A combinatorial strategy is adopted by (CN VII), the glossopharyngeal (CN IX) nerve (posterior
the biological system (Gupta et al., 2015; Korsching, 2001; tongue), and the vagus (CN X) nerve (root of tongue and
Manzini et al., 2014). Most odor molecules are recognized esophagus). The maxillary and mandibular branches of the
by more than one receptor and most receptors recognize trigeminal nerve (CN V) mediate touch, pain, temperature,
several odors that may be related by some properties such and other somatosensory sensations throughout the nasal
as the size, shape, and charges associated with functional and oral epithelia—that is, coolness and fizziness. The
groups on the molecule. A particular odor molecule may taste fibers integrate information from taste buds and relay
also consist of a number of these “epitopes” or “determi- this information to the nucleus of the solitary tract of the
nants” that possess some of these features. Thus the recog- brainstem. The primary taste cortex contains neurons that
nition of an odorant molecule depends on which receptors respond best to sweet, sour, bitter, salty, and umami-tasting
are activated and to what extent. agents, as well as neurons responsive to touch and smell.
While taste sensations have been described for many It has direct reciprocal connections with the frontal tempo-
centuries, it is only comparatively recently that the fun- ral, parietal, entorhinal, and orbitofrontal cortexes and other
damental mechanisms underlying taste transduction were cortexes. The entorhinal and orbitofrontal cortex functions
Electronic Noses and Tongues in the Food Industry Chapter | 1 7

FIGURE 1.2 The tongue showing fungiform, foliate, and circumvallate papillae. These contain taste buds containing a number of sensory cells;
membrane-bound receptors—sweet taste and umami are transduced by heterodimers of T1R2 and T1R3 subunits, and T1R1 and T1R3 subunits, respec-
tively, while bitter taste is transduced by T2R receptors (not shown). Sour taste involves activation of a type of transient receptor potential channel (TRP),
while salt taste is transduced via epithelial sodium ion channels in the cell membrane. The signals from taste buds project to the solitary nucleus of the
brainstem, and then is processed by higher regions of the brain.

to interpret tastes and includes memory and cognition. The affinities, so exhibit broad selectivity in terms of ligands
insular cortex is associated with conditioned taste aversions. that can be detected.
The cell membranes of the taste bud cells contain a va-
riety of ion channels that are involved with signal transduc-
tion. Salt taste is transduced via an epithelial sodium ion 1.3 ELECTRONIC NOSES AND TONGUES
channel (ENaC) that is ubiquitously expressed and function-
1.3.1 Electronic Noses
al in the anterior part of the tongue. Sour is the taste of acid,
that is, protons (H+). This taste is complex and is transduced So-called “electronic noses” comprise a vapor sampling
through transient receptor potential (TRP) ion channels, but system, an array of chemical sensors, and a method of sig-
there may at least three possible receptor mechanisms: H+ nal processing that leads to classification of the responses
blocks K+ ion channels, H+ ions go through ENaC channels, of the chemical sensors. The sensors in an electronic nose
or H+ ions go through a proton channel. are desired to have a broad selectivity rather than being
Sweet and umami receptors are heteromeric receptors specific to one type of volatile chemical. The human nose
made up of a combination of different subunits, coded for by can identify many odors that may contain hundreds of indi-
a small gene family—T1R. Sweetness receptors are a com- vidual chemical components and, therefore, the sensors for
bination of two types of receptor subunits (T1R2 + T1R3) an electronic nose should be generalized at the molecular
and umami receptors a combination of another set of recep- level. The desired properties for sensors are high sensitiv-
tor subunits (T1R1 + T1R3) (Doty, 2012). The bitter re- ity, rapid response, good reproducibility, and reversibility
ceptors consist of taste-2 receptors (T2Rs). Fifty to eighty to large numbers of chemicals. It is also better for an elec-
members are expressed in small subset of all taste papillae. tronic nose to be small in size and flexible, able to adapt to
T2Rs are membrane bound proteins that are bitterness re- being exposed to many types of environments, and operate
ceptors (Meyerhof et al., 2011). We still poorly understand at ambient temperatures. The working principle of these in-
taste, and other types of receptors that are under investiga- struments is based on the employment of an array of differ-
tion include those involved in the taste of fats (DiPatriz- ent nonselective chemical sensors. Each sensor in the array
io, 2014; Passilly-Degrace et al., 2014). It is clear however is able to detect a range of different odors, not just one,
that like olfactory receptors, taste receptors are capable of with a sensitivity that is different from the sensitivity shown
interacting with many types of substances with different by the other elements of the array. Such features make the
8 PART | I The Electronic Nose

FIGURE 1.3 Electronic nose concepts: sampling, sensor array, signal processing, pattern recognition.

response of the electronic nose dependent on the whole of different sensors chosen to respond to a wide range of
range of chemical information contained in an odor. This chemical classes and discriminate mixtures of volatile com-
is something similar to what occurs in biological olfaction. pounds that make up an odor. The outputs from individual
Usually, gas sensors are categorized based on their trans- sensors are processed in such a way in order to produce
duction principle and sensing material. Many different types a distinct response pattern reflecting the relative responses
of sensor technologies have been so far deployed (Gutierrez of all the sensors in the array to a given chemical stimu-
and Horrillo, 2014; Vergara and Llobet, 2011; Wilson and lus. Identification and classification of an analyte mixture
Baietto, 2009)—these include metal oxide sensors, conduct- is accomplished through comparison of this electronic fin-
ing polymers, optical sensors, piezoelectric sensors, electro- gerprint of sensor responses against previously learned pat-
chemical sensors, field effect transistors (Feng et al., 2014), terns (Fig. 1.3). Unlike conventional analytical instruments,
and more recently olfactory biosensors containing either ol- there is no need for separation of a complex mixture into
factory receptors (Ault and Broach, 2006; Du et al., 2014) individual components and this holistic approach resem-
or odorant-binding proteins (Di Pietrantonio et al., 2013; bles the process found in biological olfaction. Importantly,
Pelosi et al., 2014; Persaud, 2012) have been utilized. The these devices give information that allow comparison or
interaction with an analyte induces a physical and/or chemi- discrimination of odors without necessarily having to do a
cal change in the chemical sensing layer, which produces a chemical analysis of individual components in the mixture.
signal. The nature of the transduction processes utilized by There has also been a blurring of instrument technologies
these sensors may include electrical measurements, includ- where “electronic nose” concepts are combined with tradi-
ing changes in current, voltage, resistance or impedance, tional analytical instruments; for example, a chromatogram
electrical fields, and oscillation frequency. Other transduc- may be treated as a set of virtual sensors, or direct injection
ers involve measurements of mass changes, temperature of a mixture of substances into a mass spectrometer with-
changes or heat generation. Optical sensors measure the out prior separation will produce a complex spectrum that
modulation of light properties or characteristics such as can be processed as a “fingerprint” to describe that mix-
changes in light absorbance, polarization, fluorescence, ture (Crespo et al., 2012; Moon et al., 2014). Taking this
and other optical properties. These have been extensively to the opposite extreme, modulation of a single sensor can
reviewed in other publications (Di Natale et al., 2005, 2009; produce a virtual sensor array—for example, modulating
Walt and Sternfeld, 2006; Walt, 2010) and will not be de- the operational temperature of a single metal oxide sensor
scribed in detail here. The choice of sensor is often appli- can process a complex response that can be deconvoluted
cation dependent and are based on response and recovery (Amini et al., 2013; Herrero-Carron et al., 2015). On the
times, sensitivities, detection range, operating limitations, other hand, large arrays of sensors consisting of up to 4096
physical size, robustness to being poisoned, power con- sensors have been described and these start to resemble
sumption, and other factors. However, very few types of more realistically the olfactory receptor system (Beccher-
chemical sensor available respond specifically to a single elli et al., 2010; Bernabei et al., 2012).
chemical—they tend to show cross-sensitivity to a variety While a number of companies were formed to exploit
of chemicals, but the range of selectivity can be tailored “electronic nose” technologies over the last few decades,
so that each type of sensor responds to a different range of the majority of these have failed. One reason is “oversell-
chemicals. This inherently poor selectivity can be utilized ing” of what such devices can actually do. In fact they are
to advantage when sensors of different type are combined not analytical instruments and neither are they even close
into an array. The cross-reactive sensor array is composed to the functionality of the biological nose (Boeker, 2014).
Electronic Noses and Tongues in the Food Industry Chapter | 1 9

Another problem has been that of calibration of such instru- consistent results from such devices—especially when mea-
ments, and that of “drift” over time. The latter is associated suring a complex matrix such as food—much care needs to
with limitations of the sensor technologies utilized—chang- be taken and in fact one complaint often heard is the amount
es in responses over time due to aging, poisoning, or envi- of work required for method development for a particular
ronmental factors, together with changes in the chemical application. The techniques that are used are those that have
analytes that are being assessed. For example, a typical food been well developed over the years for gas chromatogra-
product will change organoleptic characteristics over time phy and have been adapted for “electronic nose” detectors
due to aging, decomposition, or other factors, and different (Feng et al., 2014; Pillonel et al., 2002).
batches of a product may have large differences in odor or The simplest technique consists of placing the sample
flavor. Nonetheless, there have been real successes in the into a vial that is then closed and allowing equilibrium to be
use of these technologies in the food industry that shall be reached between the matrix and the vapor phase. This “stat-
described later. ic headspace” of the vial then constitutes the sample that is
The performance of today’s artificial systems is far from introduced into the “electronic nose” system. The sample
that found in biological olfaction. The better performance of temperature, equilibration time, vial size, and sample quan-
the latter is due to the great number of receptor neurons and tity are parameters that have to be optimized for a particular
to the unique architecture of the olfactory pathway, where application and often this can be automated.
three main elements, the olfactory epithelium, the olfactory Instead of a generating a static headspace, the sample
bulb and the olfactory cortex, are completely integrated. In may be placed into a vial and in this case the vial is purged
the artificial olfactory devices, similarly to the brain, the with a continuously flowing gas stream. This in effect strips
signals coming from the sensors are processed in order to volatile components from the matrix of the sample as there
classify odors. However, this process is carried out using is a displacement of the equilibrium between the sample
mathematical tools. An initial sensor signal preprocessing matrix and the headspace. This “dynamic headspace” has
is often performed. Different preprocessing metrics can be been used to good effect in many applications. The flow
used with different aims. For example, the time dependence rate of the gas and the sample temperature needs to be opti-
of the signal can be removed in order to reduce the amount mized for a particular application.
of data that needs to be handled during the phase of pat- Often the concentrations of volatile components from
tern recognition. Linearization of the sensor response can a sample are very low, and the dynamic headspace method
be performed when the intensity of the odors is important, may be combined with a preconcentration method such as
as the sensor response is often nonlinear with increasing “purge and trap” where the vapor is trapped on an adsor-
concentration of analyte. Data reduction techniques, such as bent such as activated carbon, polymers, or inorganic ma-
principal component analysis (PCA), imitating the massive trices. After sampling the dynamic headspace over a period
convergence of the ORNs to the glomeruli, can also be ap- of time, the trap is heated to a high temperature in order to
plied to the whole sensor array response, in order to reduce discharge the trapped volatiles as a bolus into the electronic
the data dimensionality (Pearce, 1997a,b). nose. The flow rate of the gas, the purge rate, and the desorp-
The data resulting from this first processing step, or tion temperature are parameters that need to be adjusted for
coming directly from the sensors without any pretreat- a given application (Chai et al., 2008; Chen et al., 2015; del
ment, are subjected to pattern recognition (PARC) analysis Nogal Sanchez et al., 2014; Feng et al., 2014; Lopez-Feria
to obtain discrimination and/or classification. During this et al., 2008; Pillonel et al., 2002; Plutowska et al., 2011).
phase, the sensor patterns are compared to known odor pat- Solid-phase microextraction (SPME) introduced by
terns, which have been stored in a knowledge base during Pawliszyn et al. (2012) and Pawliszyn (2012) and stir-bar
a previous training stage of the device, and, using any of adsorption (SBE) are convenient methods that are used to
the many classification techniques available, identification preconcentrate a static headspace (Baltussen et al., 2002;
of the stimulus is carried out. Existing sensor arrays imple- David and Sandra, 2007). In the former a silica fiber coated
ment the broad and overlapping sensitivity feature exhib- with an organic polymer is introduced into the headspace
ited by biological receptors, but it has not yet been possible and this sorbs volatile components from the headspace and
to achieve the same dimensionality and redundancy level entraps them. A range of sorbent coatings are available that
available in the olfactory epithelium. Current chemical sen- range from hydrophilic to hydrophobic so some selectivity
sor arrays, either homogeneous or heterogeneous, have few in what is extracted from the headspace is under control of
sensing elements when compared to natural noses. the user and can be adapted to a particular application. SBE
uses a similar principle but contains a much larger adsor-
1.3.2 Sampling bent surface allowing much greater quantities of volatiles
to be entrapped. Just like the purge-and-trap method, the
Apart from sensing aspects associated with “electronic nos- SPME or SBE is heated to a high temperature to desorb
es,” the sampling aspects are often neglected. In order to get volatiles into the electronic nose detector. A variation of
10 PART | I The Electronic Nose

FIGURE 1.4 Solid-phase microextraction of a headspace and desorption process of an SPME fiber on to an array of sensors.

this technique uses a needle where the inner surface is coat- RT


ed with an adsorbent and the vapor is drawn through the E = E0 − ln Q (1.1)
nF
needle to be entrapped. Fig. 1.4 shows the introduction of
an SPME fiber into an array of metal oxide sensors for elec- where, E represents the observed cell potential at zero cur-
tronic nose applications. rent, E0 is the standard cell potential, R the universal gas
Apart from these common sampling techniques, spe- constant, T the absolute temperature in Kelvin, n is the
cialized systems exist that are dependent on the detectors charge number of the electrode reaction, F is the Faraday
that utilized in the “electronic nose”; for example, for direct constant, and Q is the ratio of ion concentration at the an-
inlet mass spectrometry, a membrane is inserted between ode to ion concentration at the cathode. They include ion
the sample and the inlet of the mass spectrometer, allowing selective electrodes. The selectivity of these electrodes is
controlled introduction of sample volatiles directly into the described by the Nikolsky–Eisenmann equation, Eq. (1.2),
ion source. Sampling techniques are reviewed by Rubiolo
et al. (2010).
RT  
ln ai + ∑ ( kij a j ) i j 
z /z
E = E0 + (1.2)
zi F  
1.3.3 Electronic Tongues j

In principle, “electronic tongues” function in a similar where ai and aj are the activity of the primary ion and in-
way to the “electronic nose” (Fig. 1.5). A sensor array terfering ion, respectively; k is the selectivity coefficient;
produces signals that are not necessarily specific for any E0 is the sum of the standard potential of the electrode and
particular chemical species. A pattern of signals is gener- the junction potential; E is the potential difference for the
ated, that can be correlated to certain features or qualities electrochemical cell composed of the ion selective and ref-
of the sample. In this case the sensors operate in an aque- erence electrode; and zi and zj are charge numbers of the
ous environment and they have different cross-sensitivities primary and interfering ion, respectively.
to various chemical species. Just like the “electronic nose,” Because the matrix containing the analytes of interest
an appropriate method of multivariate analysis or pattern may be very complex, the biggest problem encountered with
recognition is used to process the signals from the array in “electronic tongues” is that of electrode fouling. Potentio-
order to discriminate or classify different samples. As with metric measurements are temperature dependent, and the
“electronic noses,” a wide variety of sensor technologies signals may be influenced by solution changes, as well as
may be employed. These include conventional ion selec- adsorption of solution components on membrane surfaces,
tive electrodes, chalcogenide and oxide glasses, noble met- that can affect the nature of the charge transfer. Hence, care
als, organic polymers, biosensors, ISFETS, optical sensors, needs to be taken to control the temperature of the measure-
mass sensors, impedimetric sensors, and others (Baldwin ment, washing of the electrodes with solvents to minimize
et al., 2011; Legin et al., 2004, 2005; Vlasov et al., 2008, the effects of adsorption, using antifouling membranes.
2010; Winquist et al., 2004). The most common sensors However, potentiometric measurements are widely used
used are potentiometric in nature, producing an electri- because of their simplicity. Toko and coworkers (Tahara
cal potential described by the Nernst equation, Eq. (1.1), et al., 2013; Tahara and Toko, 2013; Toko, 2004, 2014;
Electronic Noses and Tongues in the Food Industry Chapter | 1 11

FIGURE 1.5 Electronic tongue concepts: sampling, sensor array, signal processing, pattern recognition.

Toko et al., 2014) developed a taste sensor array based on fundamental statistical distributions of data. Two types of
electrodes using a lipid/polymer membrane for the trans- nonparametric learning or classification methods are avail-
ducer. The composition of the membrane is designed con- able: supervised and unsupervised. Supervised methods in-
sidering the charges on the membrane surface and hydro- volve the learning of data based on advance knowledge of
phobicity on the basis of physicochemical properties of the classification, whereas unsupervised methods make no
substances with each basic taste, and as a result the system prior assumption about the data.
correlates well with basic taste perception. However, it must Preprocessing of data is often necessary before pattern
be realized that these systems in no way resemble the bio- recognition algorithms can be applied. This may involve
logical tongue. Unlike the case with potentiometric sensors, scaling of data, normalization, removal of redundant data,
voltammetric measurements are performed when equilib- extraction of features that are important to classification, and
rium is not reached, and the signal obtained is the current– others (Raman et al., 2011; Roeck et al., 2008). If the data
potential relationship. These methods are particularly use- are high dimensional, for example, when there are a large
ful when trying to obtain measurements from samples that number of sensors in an array, or if virtual sensors are be-
contain redox species. ing utilized from a mass spectrometer or gas chromatograph,
Just like with electronic noses, attention needs to be then principal components analysis is a powerful tool for data
paid to sampling—often static measurements are carried reduction. It involves forming a covariance matrix between
out, where the electrodes are inserted into a medium and an variables, and then carrying out a transformation that results
equilibrium is allowed to be established. On the other hand, in extracting eigenvectors and eigenvalues. This analysis pro-
dynamic flow of analyte medium past the electrodes may duces principal components that are a linear combination of
also give useful information. the original variables. Many algorithms are described in the
literature that are applicable to the classification problems en-
countered using electronic noses and tongues—they include
1.4 PATTERN RECOGNITION independent component analysis (ICA) and linear discrimi-
For both “electronic noses” and “tongues,” pattern recog- nant analysis (LDA), learning vector quantization (LVQ),
nition algorithms play a large role. The notable advantage self-organizing map (SOM), artificial neural networks of
is the ability to characterize complex mixtures without the a variety of architectures (feed forward–back propagation
need to identify and quantify individual components, with- networks, radial basis functions, support vector machines,
out the need of highly selective sensors. There are two main genetic algorithms, and others). All of these methods func-
approaches to pattern recognition: parametric and nonpara- tion well, but are dependent on the stability of the sensor re-
metric. Parametric methods rely upon obtaining or esti- sponses over time, and consistency in sampling. The strategy
mating the probability density function of the parameters is to expose the sensor array to a range of different analytes,
used to characterize the response of a system. Conversely, memorize the resulting patterns in a data base, and use this
nonparametric methods require no assumption about the a priori knowledge to recognize unknown samples later on.
12 PART | I The Electronic Nose

1.5 APPLICATIONS TO THE FOOD 1.6 CONCLUSIONS


INDUSTRY Electronic noses and tongues have undergone great develop-
There are a huge number of published applications of elec- ments over the last few decades. The availability of a large
tronic noses and tongues in the food industry. These have range of sensor technologies, combined with advances in
been extensively reviewed (Ciosek and Wroblewski, 2007; microelectronics, signal processing software, chemometric
Escuder-Gilabert and Peris, 2010; Peris and Escuder- and neural network pattern recognition algorithms, together
Gilabert, 2009) and it must be noted that many successes with associated methods for correcting drift in sensors and
are reported in monitoring the quality of foods, beverages, systems, have increasingly made such systems more ro-
and pharmaceuticals. The tasks typically carried out are bust. Such systems have now become hybrid—fusing many
detection and discrimination. They include monitoring the types of data together to produce outputs that can now be
quality of black tea, green tea, alcoholic beverages, adul- correlated with human sensory perception. Increasingly we
teration of olive oil, rancidity of meat, fruit ripening, and shall be seeing more and more applications of such systems
others. However, it must be also said that many of these in “online” or “at line” applications in the food industry en-
studies are not readily repeatable, and each researcher has suring quality and safety of such products.
had to carry out extensive method development where the
answers to specific questions could be determined. One ex- REFERENCES
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important findings in terms of correlation of electron- Bushdid, C., Magnasco, M., Vosshall, L., Keller, A., 2014. Humans
ic noses and tongues with human sensory perception. can discriminate more than 1 trillion olfactory stimuli. Science 343
Haddad et al. (2010) did an interesting experiment. They (6177), 1370–1372.
set out to determine whether electronic nose measure- Chai, X., Fu, S., Mo, S., Wan, S., Zhu, J., 2008. Static headspace-gas chro-
ments can be linked to olfactory perception. There is matography. Prog. Chem. 20 (5), 762–766.
evidence that the primary perceptual axis of human olfac- Chen, P.S., Tseng, Y.H., Chuang, Y.L., Chen, J.H., 2015. Determination
tion is odorant pleasantness. This is reflected in part in of volatile organic compounds in water using headspace knotted hol-
the physicochemical structure of odorant molecules. They low fiber microextraction. J. Chromatogr. A 1395, 41–47.
tested a hypothesis that an electronic nose can be tuned Chiu, P., Lynch, J.W., Barry, P.H., 1997. Odorant-induced currents in intact
patches from rat olfactory receptor neurons: theory and experiment.
to the pleasantness scale, and then used it to predict the
Biophys. J. 72 (3), 1442–1457.
pleasantness of novel odors. They found that their system
Ciosek, P., Wroblewski, W., 2007. Sensor arrays for liquid sensing—
consisting of an array of 16 sensors was able to generate
electronic tongue systems. Analyst 132 (10), 963–978.
pleasantness ratings with greater than 80% similarity to Cole, M., Covington, J.A., Gardner, J.W., 2011. Combined electronic nose
human ratings and with above 90% accuracy in discrimi- and tongue for a flavour sensing system. Sensor. Actuat. B 156 (2),
nating pleasant from unpleasant odors. 832–839.
Electronic Nose in Dairy Products Chapter | 3 25

TABLE 3.1 Overview of Electronic Noses Collected from the Literature


Sensor No. of Sample Data
Type Sensors ­Introduction Layout Commercial ­Processing Purpose References
MOS 6 Samples collected Series Yes PCA, CA Discriminate cows Elliott-Martin
by an especially with ketosis et al. (1997)
designed breath
sampler
CP 14 Headspace flushed — Yes DFA, CA, Separate Magan et al.
PCA, ANN unspoiled from (2001)
microbial spoiled
milk
MOS 4 Sensors 3 cm No, Taguchi PCA Milk quality Sivalingam
above milk surface sensors and a control by and Rayappan
ZnO home- detecting off- (2012)
made flavor
BAW 6 Headspace Series No PCA Discriminate Ali et al.
sampling by contaminated (2003)
plunging a syringe milk
CP 12 Headspace — Yes DFA Classification of Korel and
milk according to Balaban
microbial counts (2002)
MOS 18 Headspace — Yes Norms Milk shelf life Labreche et al.
injection of ­sensor (2005)
responses, PCA
CP 28 Headspace and — Yes LDA Grouping milks Biolatto et al.
stopped flow by the season (2007)
MOSFET, 10 MOS- Headspace after — Yes DPLSR, ANN Separation of Eriksson et al.
MOS, IR FET, 12 incubation at 60°C healthy milk from (2005)
CO2 MOS, 1 IR mastitic cow milk
MOS 4 or 5 Headspace Series No PCA Separation Capone et al.
stripping of UHT and (2000, 2001)
pasteurized milk;
separation by
rancidity levels
BAW 8 Headspace Series No PCA Separation of Di Natale
injection spoiled milk sam- et al. (2000)
ples; not able to
separate UHT and
pasteurized milk
MOS 10 Headspace flushed — Yes PCA, LDA Separate UHT Brambilla and
milk in normal Navarotto
and anomalous (2010)
odor
MOS 7 Headspace flushed Series No, Taguchi PCA, SVM Separate milk Brudzewski
sensors neural net- from different et al. (2004)
work dairies, and by fat
content
MOS, CP 16 (11 Headspace — Yes PCA Evaluate differ- Magan et al.
selected) injection ence in aroma (2001)
between formula
and breast milk
MOS — Headspace — Yes CA Discriminate Collier et al.
injection among milks and (2003)
among yogurts

(Continued)
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CHAPTER I.
THE MANSE AND ITS INMATES.

“But how the subject theme may gang,


Let time and chance determine;
Perhaps it may turn out a sang,
Perhaps turn out a sermon.”—Burns.

A N eminent artist, a member of the Royal Scottish Academy, who,


although well up in the seventies, and feeling many of the
infirmities of advanced age, still continues to enrich the world by
as charming landscapes and crisp sea-pieces as he produced in his
younger days, was showing me some of his sketches from nature,
many of them bearing traces of repeated handling. His face
brightened up when a well-thumbed favourite was lighted on
amongst the promiscuous contents of the old portfolio. With his eye
fixed on the sketch, and his hand moving as if either the pencil or the
brush were in it, he told with animation where he made this sketch or
took that “bit.”
“Ah!” said he, “painting is a difficult, a very difficult
thing; in fact, it’s just made up of ‘bits’—just bits. A THE
something takes your eye,—a nook, a clump of trees, ARTIST
often a single tree, a boulder, or rocks (grand effects of AND HIS
light and shade on rocks)—ay, even the shape or tinge “BITS.”
of a cloud. Well, to work you go, and down with it.—There,” said he,
as he lifted what seemed a mere scrawl on a half-sheet of old note-
paper, “I took that at the Bank door. I was struck with the effect of the
sunlight on water falling over a barrel that a man was filling in the
river, and thought it would make a nice picture. I got that bit of paper
out of the Bank, took off my hat, laid the paper on it, sketched it off in
—oh! less than five minutes, and put it on canvas next day. There’s
another. I did that bit on the leaf of my fishing pocket-book at
Makumrich, near old Gilston Castle. Now there,” said he, taking up a
rough-looking, unfinished sea-scene in oil, “that has been a very
useful bit. I was sketching North Berwick Harbour, when all at once I
was struck with an effect of light and shade on the sea. I was able to
hit it exactly;” and as he said this, he moved his head from side to
side and scanned the picture, saying, “That bit has been of great use
to me, although I have never made a finished picture of it. The
‘effect,’ the gleam, the tone are as nearly perfect as possible. Ah,”
continued he, laying down the sketch, and turning to his easel, on
which lay a snow scene,—an old thatched cottage, in my opinion
quite finished,—“now there’s lots of bits to work up in that picture.”
And sometimes shaking his brush, and sometimes whirling it in a
very small circle close to the picture, but never touching it, he said,
“There—and there—and perhaps there. Ah! nobody would believe
what a labour it is to make a good picture, with all the bits and bits!”
I am but an aspirant in literature, and would never presume to
compare myself with the veteran artist, or think that I could ever
arrange my bits of village gossip and incident with the artistic skill
which has earned for him the order of merit that he has so
honourably won and so worthily wears, but I confess to a desire to
present some of the bits of the everyday social life of Blinkbonny in
such a form as to give my readers an idea of its lights and shadows.
Blinkbonny is more of a village than a town, although it is generally
spoken of by the outside world as a town, owing to its having its
small weekly market and occasional fairs. It lies fully thirty miles
inland from Edinburgh, and is the centre of a good agricultural
district, with a background of moorland and hills. My father was a
merchant in it,—a very general merchant, as he dealt in grain, wool,
seeds, groceries, cloth, hardware, and various other commodities.
This may seem a strange mixture in these days of the division of
labour and subdivision of trades, but such dealers were not
uncommon fifty years ago, and they were frequently men of
considerable capital and influence. My elder and only brother was a
partner with my father in the business; and as I had early expressed
a desire to be a minister, I was sent to Edinburgh to prosecute my
studies in that direction, and had completed my fourth session at
college, when the death of my brother rendered it necessary that I
should do all in my power to supply his place.
I had been but a few months at home, when my father,
whose health had been failing for some years, became THE
a confirmed invalid. My brother’s death had not only FOLKS AT
affected his spirits, but injured his health, and within GREENKN
OWE.
little more than a year after this heavy trial the old man
was laid beside his wife and eldest son in the churchyard of
Blinkbonny. My sisters, all of them older than myself, were married,
excepting Maggie; and about a year after my father’s death Maggie
became Mrs. McLauchlan, so that I was left a very young inmate of
Bachelor Hall. When I had time to feel lonely I did so, but the
demands of business kept me thoroughly employed; and although I
joined habitually in the socialities of the neighbourhood, I did not
seriously think of getting married until I was called on to act as
bridegroom’s man to my schoolfellow and college companion, John
McNab, now the Reverend John McNab. He married Mary Stewart of
Greenknowe, the daughter of a small proprietor on the outskirts of
our village. Her sister Agnes was bridesmaid, and we were
necessarily brought a good deal into one another’s society. I had
often met her before, and liked her in a general way, but at her
sister’s marriage I came fully under the influence of her charms.
There was something—well, something—I cannot describe it by any
other word than just “something”—that fairly possessed me. For
days afterwards she was in my head, in my dreams, in my heart. I
will not describe our courtship; it was neither long nor romantic. I
wooed and won her, got Mrs. Stewart’s consent, and on New Year’s
Day 1841 we fixed that our marriage should take place in the last
week of January.
Mrs. Stewart felt the cold weather severely, and could not venture to
call at the manse to request Mr. Barrie, our worthy parish minister, to
perform the ceremony. She asked Agnes to go in her stead, but
Agnes could not muster courage to do so—she even felt too shy to
write to Mr. Barrie; so, although it was not exactly according to the
strict rules of etiquette I promised to call on Mr. Barrie next day, and
to arrange the matter with him.
Blinkbonny. (Page 6).
The manse stood on the top of a piece of slightly rising ground,
about a quarter of a mile to the south-west of the village. The
situation was a pleasant one. It commanded on three sides
extensive views of a well-cultivated country, backed by high and
picturesque hills; the village bounded the view on the north-east.
Near the manse stood the neat church, surrounded by the
churchyard. There were also a park of about four acres, a garden
covering nearly an acre, and some outhouses, the whole enclosed
by a compact wall.
I had been on intimate terms with all the inmates of the
manse, from Bell, the only and worthy servant, THE
upwards; but my errand made me feel rather INTERRUP
confused, and instead of the usual off-hand remark to TED CALL.
Bell, varying from, “Weel, Bell, hoo’s a’ wi’ ye?” to
comments on the weather or crops, as suited the season, I bluntly
asked if Mr. Barrie was engaged. There was a flavour of tartness in
Bell’s manner as she replied, “Mr. Barrie’s aye thrang, but he’s aye
ready to see onybody that wants him partic’larly. I’ll speir at him if
he’s engaged,” and she disappeared. Mr. Barrie himself came to the
door, shook hands with me with more than usual heartiness, put a
special emphasis on the happy in wishing me “a happy New Year,”
gave my hand a sort of squeeze, took a long look at me, and with a
smirk on his face said, “Come in, Mr. Martin, come in.” He had not
called me “Mr.” before, but only plain Robert; and from the blithe way
in which he showed me into the “study,” I saw that he knew my
position, if not my errand.
Our conversation was at first general, and on my side jerky. I did not
follow up intelligently the subjects he introduced, but was either silent
or rambling on quite irrelevant topics. He made a long pause,
doubtless to induce me to lead, as he evidently saw I was not able to
follow. The not uncommon weakness of Scotchmen, of trying to
conceal strong emotions even on subjects on which they feel very
keenly, was working in me. I was heart-glad at the prospect of my
marriage, and well I might; but I wished to appear very cool, so, as if
merely beginning another subject, I said in a conversational way, “I
was once thinking of getting married.” Scarcely had I finished the
sentence, when Bell announced that Sir John McLelland would like
to speak to Mr. Barrie when he was disengaged. Knowing that Sir
John was the largest landowner in the parish, and the patron of the
church, and that he was taking an active part in a church extension
scheme in which Mr. Barrie was deeply interested, I at once left the
“study,” stating that I would call to-morrow night, and made for
Greenknowe, where I was bantered by both ladies, but especially by
Mrs. Stewart, when I told about “once thinking of getting married.”
Laying the emphasis first on the once, then on the thinking, then on
both, she said, “Is that all the length you are? You should think twice
—second thoughts are often best. Agnes, if you had either called or
written as I wished, we could have had the invitations out to-day; but
perhaps Robert will take the second thought to-night, and until he
quite makes up his mind we must wait with patience.”
Next night found me at the manse door, which Bell
“answered.” I was very frank, but Bell had barely THE NEXT
digested last night’s slight, and before I had finished VISIT TO
my salutation to her she said dryly, “It’ll be the minister THE
MANSE.
ye want the nicht again?” and showed me into the
study. Mr. Barrie, after expressing regret at the sudden breaking up
of our last night’s interview, asked me if the day had been fixed. I told
him that we would prefer the last Tuesday of January, if that date
suited him. He at once said, “I’ll make it suit me;” and after noting it
in a memorandum book, he proceeded, although I had not
mentioned the name of my future wife, to speak very nicely of the
good folks at Greenknowe; of the late Mr. Stewart, who had been
one of his elders, and from whom, in the earlier years of his ministry,
he had received much useful counsel; of Mrs. Stewart’s almost
motherly kindness ever since he came to the parish; of his great
esteem for Miss Stewart (my Agnes), and of her devotion to her
father, especially in his long and last illness. He also spoke of my
late father and brother as excellent, very excellent men, said some
things about myself which I will not repeat, and taking me by the
hand, said, “Humanly speaking, your marriage promises to be in
every respect a happy event for all concerned. May God bless you
both, and make you blessings to one another, to all your circle, to the
Church, and to the world.”
I thanked him warmly, and added that I might trouble him by asking
his advice on some matters, and possibly Mrs. Barrie’s; and was
proceeding to bid him good-night, when he said, “Robert, this is an
occasion, I may say a great occasion, and you must take an egg with
us. I told Mrs. Barrie last night that you were ‘once thinking of getting
married.’ She will be delighted to learn that your second thought has
got the length of fixing the day. And, whilst I am in the habit of giving
all young bridegrooms a few quiet hints, I would like you to have a
chat with both of us. You will find Mrs. Barrie’s counsel sound and
practical, so we’ll join her in the parlour;” and suiting the action to the
word, he lifted the lamp, and asking me to follow him, made for the
snug parlour, where he announced me as “a subject of compound
interest now, not simple as before.”
Mrs. Barrie was carefully darning a stocking, which she laid on the
table as I entered, and shaking my hand with great heartiness, she
said, “I need hardly wish you a happy new year, Mr. Martin. You are
as sure to be happy as anybody can be sure of happiness in this
world. I hope you consider yourself a very lucky man?”
I made as nice a reply as I could. Mrs. Barrie repeated her
husband’s “You must take an egg with us;” and laying the half-
darned stocking into her work-basket on the back table, she looked
into a cradle that stood in the cosiest corner of the room, and seeing
that all was right there, she said, “I must see that the other little folks
are happit before I sit down,” and left the room. But before I tell of the
evening’s quiet enjoyment in the manse parlour, I will say something
about the inmates of the manse itself.
Mr. Barrie was ordained as minister of Blinkbonny in
1830, and early in 1831 he brought his young wife, till THE
then Mary Gordon, home to the manse. He was a son INMATES
of the manse, a son of the minimum stipend; when half OF THE
MANSE.
through his preparatory studies he became a son of
the Widows’ Fund. Mrs. Barrie’s parents had been in a very
comfortable worldly position for the first sixteen years of her life, but
through circumstances over which they had no control, and to which
she never referred, their means had been greatly reduced. Her
father died when she was eighteen years of age; her mother
survived her father about four years. She was thus an orphan at
twenty-two. She was twenty-five years of age when she was
married, Mr. Barrie being her senior by fully one year; and whilst she
brought to the manse “a good providing,” she brought little money or
“tocher,” as a bride’s marriage portion is called in Scotland. The
income of the minister of Blinkbonny, or, to use the church phrase,
the “stipend,” was paid partly in money and partly in grain, and
averaged about £160 yearly. The furnishing of the manse and the
minister’s library had required and received careful consideration.
Even the providing of live stock for the park, to commence with,
involved an outlay that in the circumstances was considerable; but
by Bell’s indefatigable industry and management, the cow, the hens,
the garden, and even the pig became such important sources of
supply in the household economy, that any description of the
inmates of the manse would be utterly incomplete which did not
make honourable mention of worthy Bell.
Bell had come with Mrs. Barrie as her first servant, and had grown
up as, if not into, a part of the family. She was fully the middle height,
muscular, not stout but well-conditioned, had a good complexion, a
“weel-faured” face, keen, deep-set, dark eyes; and altogether she
was a comely woman. I believe her full name was Isabella Cameron,
but she was only known as Bell, occasionally Mr. Barrie’s Bell; so
much so that when a letter came to the manse, addressed “Miss
Cameron,” both Mr. and Mrs. Barrie had laid it aside, expecting that
some stranger would call for it, and were instructing Bell to return it
to the post office in the evening, should no Miss Cameron cast up,
when Bell said, “My name’s Cameron; it’ll maybe be for me.” It was,
much to Mrs. Barrie’s embarrassment, and told of the death of Bell’s
aunt. Bell had few relations,—none that seemed to care for her, and
consequently none that she kept up intimacy with.
She was a year older than Mrs. Barrie. Her first “place”
had been in a small farmhouse, where the manners BELL OF
were very primitive, and the work was very constant. THE
MANSE.
One of her questions shortly after coming to the
manse was, “Does Mr. Barrie aye take his dinner with his coat on?” a
thing she had not seen before. Mrs. Barrie had a little difficulty in
getting her to understand the proprieties, but none in getting her to
do exactly as she was told. Bell felt nothing a bother, took pleasantly
any explanation given as to her mistakes, laughed at them when
pointed out, and with a cheerful “I’ll mind that,” thanked Mrs. Barrie.
It took her some time to learn the distinctive tones of the bells, the
parlour, dining-room, front door, etc.; and for the first week or two,
when a bell was rung, she ran to the nearest room and tried it, then
to another, sometimes to the disturbance of the folks inside; but she
soon came to know them.
It was a sight to see Bell unbuckle her gown,—which when at work
she gathered round her, and fastened in some wonderfully fast-loose
way,—shake herself, and stalk off in response, especially to the front
door, to any ring that seemed peremptory.
Sir John McLelland was making his first call after the marriage. He
handed Bell his card, politely asking at the same time if Mr. and Mrs.
Barrie were at home. Bell looked at the card, but it was in German
text, and therefore unintelligible. She looked at Sir John, but that did
not help her; she then turned on her heel,—the swiftest, cleverest
motion of the kind that could be imagined,—walked briskly to Mrs.
Barrie, and said, “There’s a man at the door, a weel-put-on man, and
he asked for you; an’ he gied me a ticket, an’ he’s there yet.”
Mrs. Barrie soon put such mistakes right. She found Bell an apt
scholar, scrupulously clean, sterlingly honest, and always busy,
though not fussy. At first Bell was most at home among the hens,
cows, pigs, and in the garden, but she soon became well up in all
household work. Even the addition of the children one by one never
seemed to tax Bell’s powers heavily. The first two, James and Mary,
were healthy, and in Bell’s homely phrase, “never looked behind
them;” but the third, “Wee Nellie,” had been from her birth “a feeble,
delicate little thing.” When she was about three years old, scarlet
fever attacked the children, beginning with Lewis, the baby. His was
a mild case; so were those of James and Mary, but Nellie’s was a
severe one. Her pulse ran very high, her little body was covered with
the bright scarlet “rash,” her throat sorely affected, her breathing
laboured and requiring more effort than the weak constitution could
spare. Mrs. Barrie and Bell were unwearied in their efforts to relieve
the poor sufferer, and gently was she passed from knee to knee in
her restless moods, gently was she laid down again, and coaxed and
humoured and waited on with unspeakably tender care.
Between Bell and Nellie there had been a special
intimacy. She had called herself “Bell’s bairn;” and as BELL AND
her age and health did not admit of her joining the WEE
other children at play, she was seldom out of the NELLIE.
kitchen, except when Bell wrapped her cosily in a
plaid, and carried her about the parks or garden, where Bell diverted
herself quite as much as the “wee whitefaced girlie,” by humouring
her childish whims, and joining in, if not provoking, her wondering
interest. And ever and anon, as Nellie expressed delight at what Bell
said, or did, or pulled, or showed, Bell would press her warmly to her
breast, and croon over words of endearment about her “wee
croodlin’ doo,” “her ain darling Nellie,” “she was Bell’s bairn,” and tell
her that when she was big she would help Bell to milk “Daisy,” and
feed the hens. The cosiest corner in the kitchen was Nellie’s
“housie.” There she would play for hours, sometimes sitting on her
little stool, and chatting with Bell “like an auld body;” sometimes
fondling her black-and-white kitten Tibby; sometimes putting to sleep
her favourite doll “Black Tam,” who, although he had neither arms
nor legs, and his trunk had by long wear lost the black paint, and
appeared as bare timber well time-soiled, still retained on his head,
which had been gouged out to imitate the woolly hair of the negro,
crescent-shaped indents of his original blackness, and his lips were
flecked with streaks of their primitive crimson; sometimes playing
with broken bits of china, drawing Bell’s attention to those with gold
on them as “Nellie’s pennies.” And not infrequently did Bell take the
wee lassie into her kindly lap, and press her to her kindly bosom,
and sing, and sigh as she sung, her favourite if not only song of the
“Bonnie, bonnie banks of Benlomond.”
It need hardly be recorded that Bell’s agony at Nellie’s illness was
only equalled by that of Mrs. Barrie,—possibly by that of Mr. Barrie,
but only possibly. She had been struck with the hectic
flush which glowed on Nellie’s face, and saw that the “WEARIN’
fever was sore on her; but she hoped against hope, AWA’.”
until on the seventh day of the illness a spasmodic
movement of the weak body, and a hazy gleam of the weary eye,
revealed to Bell that Nellie’s recovery was hopeless. The thought of
losing her came so suddenly on Bell, that she nearly broke down in
the room; but restraining herself as her eye rested on Mrs. Barrie’s
calm motherly face, intent on anticipating and ministering to the
wants of the sufferer, Bell whispered that she would “see if the bairns
were all right, and be back immediately,” and left the room. She
walked noiselessly through the lobby, at the darkest corner of it gave
two or three great “gulps,” and uttered a bitter “Oh! dear, dear.” This
was what nature demanded; this at least, more if she could have got
it; but this little snatch relieved her pent-up heart, and braced her for
further service. After seeing that the other children were right, she
glided into the sick-room, from which Mr. Barrie, with a remark or
rather a sigh about “too many breaths,” emerged as she entered.
She took the fever-tossed child gently out of Mrs. Barrie’s wearied
arms, and did her best to relieve the difficulty of breathing, so
harassing to the watchers, and so sore on the patient. Gradually the
fitful struggles became less violent; Nellie got quieter, softer,
powerless. She half opened her eyes, then closed them slowly, and
said in a faint voice, with a long eerie tone, “Bell.” Bell, half choking
with grief, bent over her and kept saying, “Yes, ye’re Bell’s bairn,
ye’re Bell’s ain bairn;” but observing her weary, weary face and
increasing softness, she looked wistfully at the invalid, then
sympathizingly at Mrs. Barrie, and, rising softly, laid the wee lamb on
Mrs. Barrie’s lap, slipped noiselessly to Mr. Barrie’s study, and
opening the door very slightly, said, “Please, sir, come ben, or the
angels will be before you!” She got another gulp as she waited to
follow him into the sick-room, and that helped her greatly. The little
darling recognised “papa,”—smiled as she lisped his name,—smiled
if possible more sweetly as she heard her mother’s voice, in
quivering accents, saying, “My ain wee wee Nellie!” and sighed
audibly, “Mamma’s wee-wee,”—she then closed her eyes, and in the
act of raising her tiny hand to her throat, it fell powerless, and Wee
Nellie was Wee Nellie no more, or rather, as Bell said, Wee Nellie for
ever.
Her delicate health and consequent helplessness, as
also her gentleness, had endeared her to Mr. Barrie. “THE
When all was over, he muttered, “She was a pleasant LAND O’
child, lovely and beautiful in her life;” and added in a THE
firmer voice, “It is well with the child, it is well.” Bell LEAL.”
lifted the little body from its mother’s lap, and laid it gently on the
bed. Her tears were streaming, but she had got the first bitter pang
over, and putting her arm on, or rather round, Mrs. Barrie’s shoulder,
she said, “Come away, mem, for a little; I’ll put all right.” Mrs. Barrie
obeyed mechanically, and was persuaded by Bell to lie down in bed.
There wearied nature asserted her prerogative, and she slept
soundly for a considerable time. When she returned to the sick-
room, all traces of illness, in the shape of couches, baths, phials, and
confusion, were away; the old crumb-cloth which had been put down
to preserve the carpet was exchanged for a clean linen drugget; the
fire was out, the fire-place filled with fir-tops; the window was open,
and the blind drawn down; here and there about the room were little
muslin bags filled with lavender-seed; and on the mantelpiece,
which, when she left, was covered with tumblers and cans and
glasses of medical stuff, overlapped with paper, or having spoons in
them to the hazard of their balance, stood three tumblers filled with
bunches of lavender; and on the bed lay all that remained of Nellie,
“dressed and laid out,” her little body making all the more
appearance that the snow-white bedcover was tightly laid over it. On
her face lay a muslin handkerchief, kept down by a bag of lavender
on either side.
As Mrs. Barrie approached the bed, Bell walked to the other side of
it, and slowly folded down the face-cloth. All traces of suffering and
weariness had vanished; the face was that of a child smiling in sleep.
“Bell,” said Mrs. Barrie, “she’s beautiful” (she had never said that
before of her or of any of her children), “beautiful,—and she’s home.
Of such is the kingdom of Heaven.” Bell tried to speak. She got the
length of faltering out, “For ever with the Lord,” when Mrs. Barrie
stooped down to kiss her “lost lamb.” Bell rather quickly folded the
face-cloth over the mouth, saying, “On the cheek or the broo, mem,
no’ on the mooth.” Although Mrs. Barrie’s frame shook as her lips
touched the cold brow, she pressed them on it lingeringly, and as
she raised herself she said, “I will go to her, she cannot return to
me.” Then, looking round the room, she said, “Bell, O Bell! I can
never repay, and I will never forget, your kindness at this time.” She
would have said more, but Bell broke down, and Mrs. Barrie broke
down, and both were considerably better when the pent-up flood of
sorrow found relief.
In the churchyard of Blinkbonny stands a little marble slab, only a
few inches above the ground bearing the following inscription:—

HELEN BARRIE
DIED 18TH MAY 1838, AGED 3 YEARS.
——
WITH CHRIST ... FAR BETTER.

“THE
The spot had no more constant visitor than Bell. The
BUTTERFL flowers that in their seasons grew round it were
Y ON A planted by her hand, and tended by her with
GRAVE.” constant care; the only difference being that in
weeding or trimming it there was not the quick,
bustling energy which she exercised in the garden, but a reverent
slowness unusual for her. She never put her foot on the sod under
which Nellie lay; and although for the first few visits she sighed
mournfully as she read the inscription (and she read it aloud to
herself at every visit), it was not long before her face lightened as
she uttered the last two words, and she would add in a cheerful
confirmatory tone, as if Nellie herself had repeated the epitaph, “Yes,
Nellie; yes, Bell’s bairn, far better; far, far better.”

“A butterfly bask’d on a baby’s grave,


Where a lily had chanced to grow;
‘Why art thou here with thy gaudy dye,
When she of the blue and sparkling eye
Must sleep in the churchyard low?’

Then it lightly soared through the sunny air,


And spoke from its shining track:
‘I was a worm till I won my wings,
And she whom thou mourn’st, like a seraph sings;
Wouldst thou call the blessed one back?’”

Mrs. Sigourney.
CHAPTER II.
A QUIET EVENING AT THE MANSE.

“Thrift made them easy for the coming day,


Religion took the fear of death away;
A cheerful spirit still ensured content,
And love smiled round them wheresoe’er they went.”

Crabbe.

I NEED hardly tell that between Mrs. Barrie and Bell the relationship
of mistress and servant was more than cordial, more than intimate,
—I can find no better word to express it than perfect. To say that
Bell knew her place is a term much too bald; she filled it, fulfilled it,
full-filled it. She was devoted to the family’s interest; her heart and
mind were in her work; she had a clear head, a strong arm, a blithe
happy manner, and an uncommonly large stock of common sense.
She had a ready “knack” of dividing the articles under
her care, by a sliding scale of her own, so as to put all BELL’S
to the best use: she laid aside some for the dining- SLIDING
room on “company” days, and even at a sudden call SCALE.
she was seldom found unprepared; some for the
parlour, to suit old and young (for there was no formal nursery in the
manse,—Bell’s room, “off” the kitchen, was best entitled to the name,
although competing claims might have been put forward by the
kitchen itself, the parlour, and even the study); some for the kitchen,
but that had not a high place in her scale; a good deal for the poor,—
plain, handy, and given in good time and with discernment. Of one
thing she was very careful, and that was, that if any food seemed
likely to spoil, it was given away before it went wrong; if any clothing,
it was given clean, and although often well patched, it was fit for
immediate use. There was a corner in the kitchen pantry with a stock
of comforts, and even luxuries, for cases of sickness, old age, or
special need. The dumb animals were studied with thoughtful care,
and they repaid it well. Everything that could be used was used
regularly and methodically.
Bell’s dress varied with her work. In the morning she
“sorted” the live stock, clad in what an artist would THE BUSY
have called a grotesque or picturesque costume, BEE.
according to the season. In winter her upper garment
was an old overcoat of Mr. Barrie’s—a “Spencer;” in summer it was a
loose-fitting jacket of striped cotton, lilac and white; her linsey-
woolsey petticoat was of the right length for such work, and all were
shaken or brushed or beaten daily. She put on her cotton “morning
wrapper,” of blue with small white spots, just before she “set” the
breakfast, and got “redd up” for the day in time to serve up the
dinner. While she had her set times for her regular work, and “turned
her hand” smartly to anything more pressing, she observed no
“Factory Act” restrictions as to her hours of labour. Very early in the
morning the clank of Bell’s “pattens”[1] was heard as she attended to
her home farm, and till far on in the evening she was working away
anxiously and cheerfully. Her rest was a change of work on week-
days. On the Sabbath afternoon she took what seemed likest a rest,
viz. a walk round the whole premises, leisurely, observant,
inquisitive, noticing everything, and mentally noting a good deal for
next week’s attention; varied by an occasional “saunter” into the
gardens of the neighbours for purposes of observation, comparison,
insight, or exchange.

[1] Pattens were a primitive form of what are now known as


overshoes, although “undershoe” defines the patten more
correctly. The upper part was made of wood, like the frame
of an ice-skate, but broader,—not unlike the frame of an
oval horse-brush; and it was put on by pushing the foot
firmly into overstraps made of leather or “girth cloth,” in the
same way as a horse-brush is fixed on a groom’s hand. The
under part was an oval-shaped ring of thin iron, measuring
about six inches long, four inches broad, and one inch deep.
There being no fastening at the back, the heel of the
wearer’s shoe made a “slip-shod” noise on the wooden sole,
which, added to the clanking of the iron soles, especially on
any pavement or causeway, produced a double-beat
“clatterin’ clatter.” To the inexperienced they were as difficult
to walk with as skates are; they kept the foot about two
inches from the ground, and were taken off before entering
the house by merely withdrawing the foot. They not only
kept the feet dry, but a “clean hoose.”

Her respect for Mr. and Mrs. Barrie was profound: they were the
handsomest couple in the parish, and many parishes might have
been gone over before a more comely, gentle, ladylike, person than
Mrs. Barrie could be met with. Bell said, “They were, if that was
possible, better than they were bonnie;” and when Mrs. Barrie told
Bell, as she often did, to rest and take things more leisurely, Bell
would say, “I like to work, mem, I like it; I canna be idle.” Mrs. Barrie’s
remonstrances were firmer on extra occasions, such as a “heavy
washing,” but Bell’s answer was, “It was naething, naething at a’;
and didna we get a grand day for drying the claes?”—or at the
“Spring cleanin’,” when her answer was, “It’s best to get all the
confusion past and by wi’t. It was a nice thing a fresh, clean hoose;
—’deed, mem, it astonishes me to see hoo much cleanin’ every
place needs, although it’s no very bad like before you begin.”
I may be dwelling too long on Bell, and it is not at all unlikely that she
may become the heroine of my story, or rather the central figure
round which the “bits” are grouped. If so, I could not wish a better,
although Bell herself had no idea that she was such a good servant,
or that she did more than her bare duty; she oftener felt she had not
done as well as she wished. She was far too sensible and busy a
woman to think much about herself; and should she read this, she
would be the first to say “she wished she had done better,—he
hasna tell’d my fau’ts.” Worthy, kindly, honest Bell!
Mrs. Barrie’s housekeeping was the admiration, to
many it was the miracle, of the parish and district. She “GIVEN TO
was a good manager, and with such a helpmate as HOSPITALI
Bell, she made her income do wonders. To the poor, TY.”
the manse was always open for judicious help; the
hospitality of the dining-room and parlour was substantial and
becoming. This was all the more astonishing from the fact that Mrs.
Barrie was “such a delightful creature,” “such a charming person,”
“quite a lady,” “a model minister’s wife,” “so accomplished,” “so
amiable,” “so frank,” “so nice,” “so attractive” (these are actual
epithets used by her friends), that the number of visitors, many of
whom were easily persuaded to become guests, was larger than
was desirable, and the consequent calls on the larder and pantry
were heavy. Indeed, this was a subject of frequent remark among
those who enjoyed the hospitality of the manse, all wondering how
ever she could manage, and many “beseeching” Mrs. Barrie not to
trouble herself about them, as they only wished a quiet chat,
although the length of many of their visits made them more like
visitations; Mrs. A. and Mrs. B. suggesting that Mrs. C. and Mrs. D.
might be more considerate, whilst Mrs. C. and Mrs. D. were
surprised at the audacious manner in which Mrs. A. and Mrs. B.
thrust themselves on Mr. and Mrs. Barrie. It was really difficult to
withstand the attractions of the manse, and Mr. and Mrs. Barrie,
more particularly Mrs. Barrie, was made a social martyr because she
was so good, and kind, and true.
It never occurred to Mrs. Barrie that her good nature and good
housekeeping were inconsiderately drawn upon by many who should
have known better. She liked to see, and to contribute to, the
enjoyment of others, preferred being active to being passive in this
matter, and was “given to hospitality” from the genuine sweetness of
her nature; and while the sigh of weariness often escaped her lips at
the close of some of the nice “sociables,” which had been prolonged
so as to interfere with domestic and other duties, she never
murmured; although she and Bell had often to encroach on the hours
of rest or sleep in order to keep everything forward, and as they
would like it.
Mr. Barrie’s broadcloth was invariably fresh-looking, and his linen
faultless. Mrs. Barrie was at all times becomingly dressed, and in the
afternoons quite “the lady, aye sae genty.” The boys and girls were
comfortably and neatly clad every day, specially so on Sabbath days,
and theirs was a happy home.
Before I began to describe the inmates of the manse, I mentioned
that Mrs. Barrie said, on leaving the parlour, she was going to see if
the “bairns were happit.” She seldom spoke Scotch, but when she
did, it was with quaint emphasis and special sweetness. There was
no real need for Mrs. Barrie having any anxiety on this subject of
“happing,” as Bell was always on the alert; but Mrs. Barrie’s motherly
heart could not rest until she had seen, and kissed in their beds, her
“wee croodlin’ doos.” She went first to see Bell about the supper;
then to Bell’s room, where Mary and Flora were fast asleep; then to
her own room, where Lewis was sleeping soundly, but James wide
awake, scheming in his little head whether he could not make a pair
of skates, and wishing that Bell would come up, as her “pattens”
seemed the likeliest raw material to make them of, and he had seen
an old pair in the byre. Mrs. Barrie heard his story, and said they
would never do; but that Mr. Martin was in the parlour, and she would
ask him the price of a pair, if he would sleep like a good boy; and
kissing both, and “tucking” them in, she returned to the parlour.
During her absence, Mr. Barrie spoke to me in quite a
fatherly way. He knew that I had a good business and BE
fair prospects, but that, since my father’s death, I had “JUDEECI
bought a small property called Knowe Park adjoining OUS.”
the village, and that this had absorbed my available
means to such an extent as to render it a little difficult for me to carry
on business comfortably to the extent that my father had done. After
stating that he thought I was taking a wise step in getting married, he
said he found it generally the case, although it sounded like a
contradiction, that a married house was more cheaply and much
better kept than a bachelor’s; and that he was in the custom of
drawing the attention of folks who were about to get married to the
subject of Life Assurance, or, if working men, to Benefit Societies,
and to the necessity of economy and prudence in money matters.
“But,” added he, “you know these things better than I do, and I know
you will act judeeciously,” with a considerable emphasis on the ee.
And as he referred to the various relationships of social life, he
closed each section (for his advices unconsciously ran into “heads
and particulars,” like his sermons), with, in short, “Be judeecious;”
and so clearly did he illustrate the inseparable connection between
wisdom and success or happiness in everything he spoke of, that his
advice seemed then, and seems yet, summed up in, “Be
judeecious.” He will excuse me for telling here, that in the parish he
was not unfrequently spoken of as “Judeecious;” and after the lapse
of fully forty years, he is still occasionally styled, “Worthy old
Judeecious,” by some elderly warm friends, when recalling the sunny
memories of former days, although in general conversation he is
now spoken of as Dr. Barrie.
He related with considerable glee a saying of an old minister, who, in
speaking of money matters, used to maintain that there were only
three ways in which a minister could make money—patrimony,
matrimony, or parsimony. He also told the story, which is long ago
threadbare, of the old merchant, who, when asked why his son had
not done so well in business as he had, replied, “That’s easily
explained: we old folks began with a little house and a plain table,
with porridge and a herring, and got up to tea and a ‘chuckie’
(chicken); but the young folks began with a braw house, and tea and
chuckies and silks, and never buckled up their sleeves to work.”
When Mrs. Barrie joined us, supper was already on the table. After
glancing into the cradle, to see if all was right with “Gordie,” or
Gordon Lennox, as his full name was, she said, “Come away,
gentlemen,” and seating herself at the head of the table, did the
honours in a graceful and homely way.
Bell had brought in the little black kettle, and it kept
singing by the fireside. When the simple meal was “BAIRNS
over, Mr. Barrie and I made a “tumbler” of toddy each, WILL BE
a rare thing for him, but he said it was “New Year BAIRNS.”
time,” and an “occasion;” and my health was drunk,
and that of Agnes, in which Mrs. Barrie joined, a very rare thing for
her; and Mr. Barrie had just said, “Now, my dear, you must give Mr.
Martin the benefit of a little of your experience,” when the door-
handle was slowly turned, evidently by a less firm hand than Bell’s,
and a little head and part of a little white nightgown, appeared at the
half-opened door, and a voice was heard timidly saying, “Mamma,”
followed by Bell’s voice, which, with a mixture of astonishment and
anxiety in its tone, was heard saying, “James—here—at this time o’

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