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Cambios Fisicoquimicos en El Cafe Durante El Tueste en Lecho Fluido - Maestría 2012 PDF
Cambios Fisicoquimicos en El Cafe Durante El Tueste en Lecho Fluido - Maestría 2012 PDF
by
Niya Wang
A Thesis
Presented to
The University of Guelph
ROASTING
processing of coffee beans using fluidized air roaster were studied. The results
higher pH value, higher titratable acidity, higher porous structure in the bean cell
tissues, and also produced more aldehydes, ketones, aliphatic acids, aromatic
showed that clusters for principal components score plots of ground coffee,
extracted by a mixture of equal volume of ethyl acetate and water, were well
members Dr. Lisa Duizer, and Dr. Massimo Marcone for their unlimited
confidence on my research work and helps during the writing of the thesis.
Canada (NESRC) and Mother Parkers Tea & Coffee Inc., for their essential
financial support, without which this research will not be possible. Many thanks to
my Packaging and Biomaterials Group sisters and brothers: Ana Cristina Vega
Alex Jensen, Khalid Moomand, Qian Xiao, Xiuju Wang, and Ruyan Dai for their
assistance, friendship, patience, and bringing colourful life for these years. Many
thanks are also going to Dr. Yukio Kakuda, Dr. Sandy Smith, and Bruce Manion
my parents, my husband Dr. Yucheng Fu, my son Stanley Fu, and other family
members for their infinite love, support and encouragement throughout these
iii
TABLE OF CONTENTS
ACKNOWLEDGMENTS.……………………………………………………….….......iii
TABLE OF CONTENTS.…………………………………………………………...…..iv
LIST OF FIGURES.………………………………………………………………...…..vi
LIST OF TABLES.…..………………………..…………………………………...…..viii
LIST OF ABBREVIATIONS.………………………………………………….…...…..ix
1 INTRODUCTION ............................................................................................... 1
iv
4.3.3 PCA Analysis of Solvent Extracts of Coffee Beans ............................. 40
4.3.4 PCA Analysis for Coffees According to Degree of Roast .................... 47
4.3.5 SIMCA Analysis ................................................................................... 52
7 REFERENCE ................................................................................................... 82
v
LIST OF FIGURES
2004)..................................................................................................................... 9
Figure 5 Air temperature (in roast chamber) profiles of the fluidized bed hot air
acetate, acetone, ethanol, and acetic acid (the right vial represent the extracts by
ethyl acetate, acetone, ethanol, or acetic acid using method #1 (with water) and
Figure 8 Selected FTIR spectra of dark roast coffee extract obtained with
Figure 9 PCA of FTIR data for hexane, dichloromethane, ethyl acetate, and
acetone extracts of medium roast coffee. Row A: Two-factor score plots. Row B:
Figure 10 PCA of FTIR data for hexane, dichloromethane, ethyl acetate, and
acetone extracts of dark roast coffee. Row A: Two-factor score plots. Row B:
Figure 11 PCA of FTIR data for dichloromethane extracts of coffee (from the
vi
same origin) with two degrees of roast. Row A: Two factor score plots. Row B:
Figure 12 PCA of FTIR data for ethyl acetate extracts of coffee (from the same
origin) with two degrees of roast. Row A: Two factor score plots. Row B: Loading
of coffee beans processed to different roast stages (A). The same data are
Figure14 PCA analysis for coffees during roasting. Column A: Two-factor score
Figure15 The expanded 2910-2850 cm-1, and 1800-1500 cm-1 regions of the
Figure16 PCA analysis for coffees collected at the same sampling point. Row A:
vii
LIST OF TABLES
(g/100g) ................................................................................................................ 7
Origins ................................................................................................................ 52
Table 8 SIMCA classification results for coffees according to degree of roast ... 53
viii
LIST OF ABBREVIATIONS
GC Gas chromatography
L* Lightness
ix
1 INTRODUCTION
Coffee is one of the most popular beverages in the world. Nearly 25 million
farmers in 50 countries around the world depend on coffee for a significant part of
their livelihoods (Cague et al. 2009). Coffee is the most traded commodity
second after oil (Ponte 2002). Among coffee drinkers, the average consumption
in the United States is 3.2 cups of coffee per day versus 2.6 cups in Canada
(Canada 2003).
quality of green beans, the roasting conditions, the time since the beans are
roasted, and the type of water used for brewing. More than 800 volatile
The overall quality and chemical composition of green coffee beans are
affected by many factors, such as the composition of the soil and its fertilization,
the altitude and weather of the plantation, the cultivation, and the drying methods
used for the beans. Coffee plants are mainly grown in tropical and subtropical
regions of central and South America, Africa and South East Asia, in temperate
and humid climates at altitudes between 600 and 2500 m (Schenker 2000). The
genus coffee belongs to the botanical family of Rubiaceae and comprises more
1
recently been introduced with success. Usually roasted coffee beans from
different origins are blended at specific ratios to provide coffee of unique flavour
profiles. Often time, coffee beans are blended for the purpose of cost saving.
Coffee cherries are harvested each year when they are bright-red, glossy,
and firm. After removing the outer hull, the seeds inside of the cherry are
commonly called "green coffee beans". The quality of the green coffee beans is
drying, crop year, and presence of defects (crack, withered bean, bean in
The unique aroma profiles of coffee are closely related to the time-
temperature profile used during roasting. The roasting profiles are chosen to
produce high quality coffee which are unique to specific brands and must be
takes place at the target process parameters. Industrial scale roasting of coffee
heated with hot gas in a horizontal drum, or vertical drums equipped with paddles.
Roasting time can range from 3 to 12 min, depending on the temperature used,
achieved by directing high velocity hot air towards the beans, usually from the
bottom of the roaster, to suspend the beans in turbulent air. The hot air
temperature ranges from 230 to 360oC (Eggers & Pietsch 2001). The roast
2
Different temperature profiles affect dehydration and the chemical reaction
conditions in the bean which control gas formation, browning and flavour
sensorial changes in the coffee beans (Clarke & Macrae 1988; Schenker 2000;
Schenker et al. 2002; Baggenstoss et al. 2008). Color change and weight loss
are frequently used as a measure of the degree of roast, and both are directly
related to the final roasting temperature (Sivetz 1991; Illy & Viani 1995). Other
methods, such as the ratios of free amino acids (Nehring & Maier 1992), and
chlorogenic acids content (Illy & Viani 1995) have also been used.
producing more aroma volatiles and higher brew yield (Schenker et al. 2002;
Lyman et al. 2003). Reviewing these and other literature, one can conclude that
the complex changes in coffee during roasting do not solely depend on physical
parameters at the start and end point of the thermal process, but rather a path-
3
of time-temperature effects on physical and chemical properties of coffee from
2 LITERATURE REVIEW
The overall quality and chemical composition of green coffee beans are
affected by many factors, such as the composition of the soil and its fertilization,
the altitude and weather of the plantation, and the final cultivation and drying
methods used. Coffee plants are grown in tropical and subtropical regions of
central and South America, Africa, and South East Asia, mainly in regions with
temperate and humid climates (Schenker 2000). Brazil is by far the largest
grower and exporter of green coffee beans in the world followed by Vietnam,
Colombia, Indonesia, Ethiopia and India – producing nearly 2.5 million tons of
comprises more than 90 different species (Davis 2001). However, only Coffea
while Robusta accounts for about 35% of the world’s production; other species
with not much commercial value like Coffea liberica and Coffea excelsa represent
only 1% (Rubayiza & Meurens 2005). Due to its more pronounced and finer
4
command higher prices (Valdenebro et al. 1999). Table 1 provides a general
survey on the chemical composition of green Arabica and Robusta coffee beans
Coffee cherries are harvested when they become bright-red, glossy, and
results in a superior product quality because only ripe cherries are selected. After
harvesting, the coffee fruits are separated from the pulp, which is carried out by
dry or wet processing (Clarke & Macrae 1987; Illy & Viani 1995). The dry process
is simple and inexpensive. The whole cherries are dried under the sun in open air,
followed by the separation of the hull (dried pulp and parchment) mechanically to
yield the green beans. On the contrary, the wet process requires greater
investment and more care, but results in a superior coffee quality. In the wet
process, the pulp of the coffee cherries, which is made up of exocarp and
beans. After drying either under the sun or in a dryer, the parchment is removed
to produce the green coffee beans. Bean size, color, shape, processing method,
crop year, and presence of defects, are some of the parameters used to evaluate
characteristic coffee aroma is developed due to the complex reactions that take
place in the beans. To develop a unique flavour, green coffee beans are roasted
5
The aroma profile of roasted ground coffee is also related to the origin and
variety of the beans. In general, blends with greater Arabica content tend to carry
more fruity notes due to the aldehydes, acetaldehyde, and propanal, while the
pyrazines give the earthy odor. In comparison, Robusta beans carry stronger
“roasty” and “sulphury” note due to the presence of greater amount of sulphur-
containing compounds (Sanz et al. 2002). Thus, Arabica is often added for the
aroma effect while Robusta is used for enhancing the body, earthy and phenolic
notes of the coffee blend (Parliment & Stahl 1995). Besides contributing to
balanced flavour profiles, Robusta coffee is often blended with Arabica for cost
reduction purpose. Robusta beans are lower in cost since the crops are more
which represent about 11-20% of coffee production, can impact the flavour of the
beans and non-defective beans. The researcher found that non-defective beans
were heavier, had higher water activity, and lower titratable acidity than the
soluble phenols were also higher in non-defective coffee beans (Mazzafera 1999).
6
Table 1 Chemical composition of green Arabica and Robusta coffee beans
(g/100g)
Water 8 to 12 8 to 12
content and stored below 26oC under dry environment (50-75% RH) to maintain
the bean quality and to prevent the growth of mould (Gopalakrishna Rao et al.
1971; Kulaba 1981; Betancourt & Frank 1983). Under optimal storage conditions,
7
green coffee beans may be stored for more than 3 years (Bucheli et al. 1998).
Usually, green coffee beans are packaged in natural jute, sisal or burlap bags,
although high quality beans may be packaged in high barrier synthetic vacuum
to detect the early stages of coffee deterioration. Bucheli and others (Bucheli et al.
1996) reported that glucose was a sensitive marker for green coffee bean quality
during storage. Glucose is present only in trace amount of good quality green
coffee, and the content will increase when deterioration occurs (Wolfrom & Patin
Green coffee beans provide neither the characteristic aroma nor flavour of
brewed coffee until they are roasted. Moreover, the roasting process increases
the value of coffee beans, by 100-300% of the raw material (Yeretzian et al.
2002). Roasting of coffee beans typically takes place at 200-240°C for different
times depending on the desired characteristics of the final product. Events that
take place during roasting are complex, resulting in the destruction of some
The chemical compositions of green, roasted, and brewed coffee are shown in
8
Green coffee beans Roasted coffee beans
soluble soluble
carbohydrates starches and carbohydrates starches and
9% pectins 10% pectins
13% water 14%
2%
water non volatile acids CO2
12% 7% 2%
cellulose
caffeine
(Hyd)
1% cellulose
13%
(Hyd)
non volatile acids 14%
protein
7%
caffeine 13%
1%
protein cellulose ash
12% (non Hyd) 4% cellulose
18% (non Hyd)
ash trigonelline oil
oil 17%
3% 1% 13% trigonelline
11% 1%
Brewed solubles
trigonelline
caffeine 4%
6%
non volatile
ash
acids
16%
31%
oil 1%
protein
5%
soluble
carbohydrates
37%
2004)
undergo moisture loss from 8-12% in green coffee beans to about 5% in the
roasted coffee beans (Illy & Viani 1998). The smell of the beans changes from
herb-like green bean aroma to bread-like, the color turns from green to yellowish,
and the structure changes from strength and toughness to more crumbly and
brittle. When the internal temperature of beans reaches 100oC, the color
darkened slightly for about 20-60 s due to the vaporization of water. At 160-
170oC, the beans become lighter in color for about 60-100 s. As roasting
9
continues at this temperature, Maillard and pyrolytic reactions start to take place,
buildup of water pressure, along with the large amount of gases generated
causes the cellulose cell wall to crack, giving rise to the so called “first crack”. As
darker and more rapid popping of coffee bean occurs (“second crack”) as the
carbon dioxide (CO2) buildup exceeds the strength of the cellulosic walls of the
bean. Finally, after roasting, the fresh roasted coffee beans are quickly cooled to
The final quality of roasted coffee is influenced by the design of the roasters
and time-temperature profiles used. Although heat transfers during roasting can
important mode of heat transfer that determines the rate and uniformity of
is almost exclusive based on convective heating can result in low density and
high yield coffee (Eggers & Pietsch 2001). On the other hand, coffees roasted in
drum roaster that involves mainly conductive heat transfer have less soluble
solids, more degradation of chlorogenic acids, more burnt flavour, and higher
loss of volatiles than the fluidized bed roasters (Nagaraju et al. 1997).
been reported by Lyman et al. (Lyman et al. 2003). They observed that the
medium roasted process (6.5 min to the onset of the first crack and 1.0 min to the
onset of the second crack) resulted in good balance of taste and aroma with
10
citrus flavour. However, the “sweated process” (4.5 min to the first crack and 6.5
min to the second crack) resulted in non-uniform bean color and the coffee was
“sour, grassy, and underdeveloped”. Reducing the heating rate further by using
the “baked process” (11 min to the first crack and 18 min to the second crack)
produced coffee of “flat, woody with low brightness and acidity” (Lyman et al.
2003). In another study, Schenker et al. reported that LHC process (150 to 240 oC
aroma volatiles, while the long time low temperature (LTLT) approach (isothermal
heating at 220oC for 600 s) generated the lowest aroma volatiles. Moreover, the
categorized as light, medium or dark roasts. Light roast process tends to give
non-uniform bean color with sour, grassy, and underdeveloped flavour, while
medium roast process produces a balanced taste and aroma with citrus flavour.
By contrast, dark roast process produces coffee of low acidity sensory profiles
parameters only allow assessment of the flavour profile for coffee roasted under
narrow process conditions (Sivetz 1991; Illy & Viani 1995). Other analytical
methods for quantifying the degree of roast include ratio of free amino acids
(Nehring & Maier 1992), alkylpyrazines (Hashim & Chaveron 1995), and
chlorogenic acids content (Illy & Viani 1995). Fobe and others (Fobe et al. 1968)
11
studied changes in chemical composition of Arabica coffee roasted at 230°C at
different process times. They reported that as the roasting time increased, the
following changes occurred: (1) sugar contents first increased, and then
continuously; (4) free fatty acids increased; and (5) unsaponifiable compounds
Roasting causes a net loss of matters in the forms of CO2, water vapor, and
organic acids and lipids, while caffeine and trigonelline (N-methyl nicotinic acid)
contents remained almost unchanged (Buffo & Cardelli-Freire 2004). The main
acids present in green beans are citric, malic, chlorogenic, and quinic acids.
During roasting the first three acids decrease while quinic acid increases as a
result of the degradation of chlorogenic acids (Ginz et al. 2000). Formic and
acetic acids yields increase up to the medium roasting degree and then begin to
in titratable acidity during roasting was observed from green to medium roast,
12
The reaction products formed are highly dependent on the roasting time-
temperature profile used. Excessive roasting produces more bitter coffee lacking
develop full organoleptic characteristics (Yeretzian et al. 2002; Lyman et al. 2003;
naturally occurring in coffee bean are lost during roasting, the formation of other
antioxidants from Maillard reactions during roasting can enhance the antioxidant
activity of coffee. Compared to medium roast coffee, dark roast coffee exhibited
lower radical scavenging activity than medium roasted coffee due to the
degradation of polyphenol, and thus the antioxidant activity will also depend on
time. They observed a distinctive increase in acetic acid, methyl acetate, and
roasting condition. For instance, at 190oC, the above observed changes took
place at 19 min but shifted to 30 min when the beans were roasted at 180 oC
13
monitor the roasting progress of coffee beans (Hashim & Chaveron 1995). It has
been suggested that the pressure buildup within intact bean cells is comparable
which have not been fully understood. Based on the literature reviewed, we can
conclude that the quality of roasted coffee cannot be solely described in terms of
physical parameters at the start and end point of roasting, but rather it is
dependent on the path taken during the roasting process. To reach a specific
flavour profile, not only that precise control of roasting time and temperature is
needed, the variety/quality of green beans, cooling, and degassing conditions are
volatile and non-volatile, some of the former being responsible for aroma and the
latter for the basic taste sensations of sourness, bitterness and astringency
peptides and free amino acids, polyamines and tryptamines, lipids, phenolic
acids, trigonelline, and various non-volatile acids in the green coffee beans were
involved in the flavour formation during roasting (Russwurm 1970). For example,
14
color, aroma, bitterness, and sourness; minor protein components like free amino
acids are highly reactive by interacting with reducing sugars, which make the
Maillard reaction, reducing sugars such as glucose or fructose react with free
melanoidins.
More than 800 volatile compounds have already been identified in roasted
coffee, among which, about 40 compounds are responsible for the characteristic
aroma of coffee (Belitz et al. 2009). Some of these compounds are summarized
in Table 2, showing the odorant groups that they are being categorized to
15
Table 2 Potent odorants in Arabica coffee from Colombia
Methylpropanal 2-Furfurylthiol
2-Methylbutanal 2-Methyl-3-furanthiol
3-Methylbutanal Methional
2,3-Butandione 3-Mercapto-3-methylbutyl-formiate
2,3-Pentandione 3-Methyl-2-butene-1-thiol
4-Hydroxy-2,5-dimethyl-3(2H)-furanone Methanethiol
(HD3F) Dimethyltrisulfide
5-Ethyl-4-hydroxy-2-methyl-3(2H)-
furanone (EHM3F)
Vanillin
2-Ethyl-3,5-dimethylpyrazine Guaiacol
2-Ethenyl-3,5-dimethylpyrazine 4-Ethylguaiacol
2,3-Diethyl-5-methylpyrazine 4-Vinylguaiacol
2-Ethenyl-3-ethyl-5-methylpyrazine
3-Isobutyl-2-methoxy-pyrazine
Acetaldehyde 3-Hydroxy-4,5-dimethyl-3(5H)-furanone
Propanal (HD2F)
(E)-β-Damascenone
5-Ethyl-3-hydroxy-4-methyl-2(5H)-
furanone(EHM2F)
following:
16
(1) Proteins, peptides and amino acids: Crude protein content is relatively
stable during roasting, while the free amino acids decrease by 30%, with dark
roast espresso reaching up to 50% (Belitz et al. 2009). Protein content plays an
important role in espresso coffee as it affects the foamability of the beverage that
the foamability increased generally with increase total protein concentration until
a maximum value is reached (Nunes et al. 1997). The composition of the amino
acids vary dependent on their thermal stability and reactions involved. For
cysteine and arginine. The latter amino acids tend to deplete rapidly during
roasting due to their involvement in Maillard browning reactions (Illy & Viani
2005).
pectins play important roles in the retention of volatiles and contribute to coffee
brew viscosity. It is reported that in espresso coffee, the foam stability is related
tocopherols and sterols contribute to brew viscosity. The lipid fraction tends to be
stable and survive the roasting process with only minor changes. Linoleic and
palmitic acids are the predominant fatty acids in coffee. Cafestol and kahweol are
17
indicator for detecting Robusta content in coffee blend (Speer et al. 1991; Belitz
et al. 2009).
physiological properties of coffee, and also in determining the strength, body and
bitterness of brewed coffee. The caffeine content of green coffee beans varies
according to the species that Robusta coffee contains about 2.2%, and Arabica
caffeine (Ramalakshmi & Raghavan 1999). However, caffeine content per 177
preparation(Rogers & Richardson 1993; Bell et al. 1996). Bell and others (Bell et
al. 1996) reported that more coffee solids, larger extents of grinding, and larger
similar to that of store-ground coffee, and boiled coffee had caffeine contents
(5) Acids: Acids are responsible for acidity, which together with aroma and
Carboxylic acids, mainly citric, malic and acetic acids are responsible for acidity
in brewed coffees. Arabica coffee brews are more acidic (pH 4.85-5.15) than
(6) Melanoidins: The final products of the Maillard reaction between amino
18
roasted coffee its characteristic color, possess antioxidant activity, and affect on
the flavor volatiles (Hofmann & Schieberle 2001; Del Castillo et al. 2002; Vignoli
et al. 2011).
source, fixed mirror, moving mirror, beam splitter, and detector (Figure 2). The
principle of the FTIR spectroscopy is that the beam splitter splits the light beam
from the IR source and sends half of the IR radiation to the fixed mirror and the
other half to the moving mirror. The split beams recombine to form overlapping
radiation waves that interact with the sample, resulting in an infrared spectrum.
19
Figure 2 Schematic diagram of a typical FTIR spectrometer
the IR region that are absorbed by a material. IR spectral regions can be divided
into three parts, which are near-IR (13000-4000 cm-1), mid-IR (4000-400 cm-1),
and far-IR (400-10 cm-1). The bonds involved in the near-IR are usually due to C-
and gaseous sample. The reflectance method can be used for samples that are
20
difficult to analyze by transmission method. Attenuated total reflectance (ATR)
salt plates used for the analysis of liquid and semi-liquid materials. Because of
the reproducible effective path length, ATR is well suited for both qualitative and
(PAS) are also very useful in analyzing samples. Micro-sampling method is used
such as a beam condenser or a diamond anvil cell can be used (Stuart 2003).
Various FTIR techniques have been used for coffee research. For instance,
FTIR has been used for caffeine determination in roasted coffee in the mid-IR
range (Garrigues et al. 2000; Ohnsmann et al. 2002), for discrimination of coffee
varieties (Kemsley et al. 1995; Briandet et al. 1996b; Garrigues et al. 2000), and
(Briandet et al. 1996a). Moreover, FTIR-ATR has been successfully used in the
which contains carbonyl vibration bands that can be used to correlate vinyl
2.6 Chemometrics
21
Chemometrics can be generally described as the application of
processes, and extract more useful information from chemical and physical
2010):
expose possible outliers, and to indicate whether there are patterns or trends in
the dataset. Principal component analysis (PCA) and hierarchical cluster analysis
interest. Partial least squares (PLS) and principal component regression (PCR)
are two algorithms commonly used for regression and are designed to avoid
previously analyzed data set, for which its categories are already known. PLS
22
Among the chemometric analyses used, PCA by far is the most commonly
et al. 2004). The goal of PCA is to visualize the inherent data structure and reveal
matrix. The new variables are linear combinations of the original ones. The
principle of PCA can be illustrated using a simple dataset, where the 3 variables
needed to describe the dataset are represented by three axes in the data-space
(Figure 4). PC1 has a direction that takes into account as much variance in the
data as possible. PC2, orthogonal to PC1, has a direction where the second
largest variance occurs. The objects are then projected down to the plane of the
two PCs. A large data-set may therefore be represented by only a few PCs,
which describe a large part of the variance in the data as a linear combination of
the original variables. PCA is very useful for solving pattern recognition problems
1990).
correlating two or more blocks of data with each other, or predicting a value of
one block by using the data from the other block that is easier to measure
(Gerlach et al. 1979). PLS can handle more than one dependent variable and is
23
In addition, it can tolerate missing values in the data-matrix (Geladi & Kowalski
coffee. Briandet and others adopted PCA to analyze FTIR spectra of coffee
extracts. They showed that 100% correct classifications for both training and test
samples for Arabica and Robusta in Instant Coffee. They also applied PLS to
predict the relative Arabica and Robusta contents in their coffee samples by
analyzing the FTIR spectra (Briandet et al. 1996a). Bicchi and others
24
chromatographic data obtained by headspace solid phase microextraction (HS-
SPME), and the results showed that coffees from different origins can be
successfully separated (Bicchi et al. 1997). In another study, Charlton and others
coffee samples obtained from three different producers (Charlton et al. 2002). In
their study, 99% of the samples were correctly classified accordingly to their
manufacturers. Also, blind testing of the PCA model with a further 36 samples of
instant coffee resulted in a 100% success rate in identifying the samples from the
three manufacturers.
25
3 OBJECTIVES
physical and chemical properties of coffee. The objectives of this study are:
Rica, Ethiopia, and Kenya) processed to medium and dark roasts, using
26
4 FEASIBILITY STUDY ON CHEMOMETRIC DISCRIMINATION OF
4.1 Introduction
Coffee is one of the most popular beverages in the world due to its unique
aroma, taste, and stimulating effects of caffeine. The quality of brewed coffee is
Liberica) and method used to process the coffee cherries (dry vs wet), the overall
quality and chemical composition of coffee bean can vary considerably. By and
large, the Arabica coffees have more pronounced and finer flavor profiles that are
considered better quality and, accordingly, command a higher price than the
Robusta and Liberica coffees (Davis 2001). The composition of the soil and its
fertilization, the altitude and weather of the plantation, and the final cultivation
and drying methods used will all affect the green bean quality (Costa Freitas &
Mosca 1999). Roasting, the final processing step before grinding and brewing,
the roasting process, the reactions that occur in the coffee bean are complex and
ground coffee due to the presence of visual clues in the former (size, shape,
defect, etc.). By contrast, these indicators are absent for ground coffees;
27
therefore, sample discriminating can be difficult. Often time, sensory evaluation
and cupping are needed (Martin et al. 1999). Analytical methods have been
(Krivan et al. 1993; Martin et al. 1999), volatile compounds (Silvia et al. 2004),
chlorogenic acids (Maria et al. 1998), fatty acids (Bertrand et al. 2008), and
used for investigating covalent bond vibration in coffee. This method has been
used to determine the caffeine content in roasted coffee (Garrigues et al. 2000;
Briandet et al. 1996b; Garrigues et al. 2000), and to detect adulteration in instant
coffees (Briandet et al. 1996a). Because of the complexity of FTIR spectral data,
chemometric analysis [e.g., PCA and SIMCA] is often used to reduce the
analyze FTIR spectral data of coffee, for instance in the chemical discrimination
of Arabica and Robusta coffees (Briandet et al. 1996b), quality control and
ethanol, and acetic acid). Our objective was to investigate the feasibility of using
28
infrared spectral data of these extracts, in conjunction with PCA and SIMCA, to
discriminate four Arabica ground coffees from different origins (Colombia, Costa
Rica, Ethiopia, and Kenya) that had been roasted to two roast degrees (medium
or dark).
4.2.1 Chemicals
Dichloromethane, ethyl acetate, acetone, and acetic acid were purchased from
Rica, Kenya, and Ethiopia were purchased from Green Beanery (Toronto,
Canada). Green coffee beans (45 g) were roasted in a fluidized bed hot air
roaster (Fresh Roast SR 500, Fresh Beans Inc., Park City, UT). Two isothermal
roasting programs were used for preparing dark and medium roast coffees
(Figure 5). The roasted beans were stored in hermetic glass bottles in the dark at
29
250
200
Roasting Temperature, o C
Medium roast profile
175
150
125
100
75
50
25
0 50 100 150 200 250 300 350 400 450 500 550
Roasting Time, S
Figure 5 Air temperature (in roast chamber) profiles of the fluidized bed hot air
coffee roaster
Roasted coffee beans were ground using a coffee grinder (Bodum Antigua
Electric Burr Grinder, Bodum, Inc., Copenhagen, Denmark) at the medium grind
setting. The color of the ground coffee was measured in the L*, a*, b* system
Inc., Osaka, Japan) in the reflectance mode. Before analysis, the instrument was
30
procedures. In the first procedure (method #1), 0.2500 g of ground coffee was
accurately weighed into a glass vial, and 1 mL deionized water was added to wet
the sample. The glass vial was shaken for 1 min with an IKA-VIBRAX-VXR
vibrator (Janke & Kunkel, Inc., Staufen, Germany) at the 200 dial setting; 1 mL of
organic solvent was added and the mixture was shaken for an additional 5 min.
The organic phase was then transferred to another vial and allowed to rest for 10
min before ATR-FTIR analysis. In the second procedure (method #2), a similar
procedure was used except that water was not added prior to solvent extraction.
The coffee extract was scanned using an FTIR spectrometer (IR Prestige-
21; Shimadzu Corp., Tokyo, Japan) equipped with a deuterated triglycine sulfate
diamond crystal (Pike Technologies, Madison, WI) was used for sampling. The
background spectrum was collected using an empty ATR cell. To collect each IR
spectrum, coffee extract (6 μL) was placed onto the ATR crystal, and the solvent
technique removed interference from the solvent signals and increased the
of solvent were different due to the different solubilities of each solvent in water.
31
replicates were scanned. Between samples, the ATR crystal was carefully
cleaned with 95% (v/v) aqueous ethanol solution, and dried with lint-free tissue
paper. The spectral baseline was examined visually to ensure that no residue
from the previous sample was retained on the crystal. All spectra were recorded
format, organized in Excel spreadsheets, and then analyzed using Pirouette v.4.0
were applied to FTIR spectra to reduce baseline variation and enhance spectral
features. Nine spectra (3 extracts for each coffee and 3 replicate spectra for each
extract) for each coffee were divided into two groups: 6 spectra from the first two
extracts were used to calibrate the SIMCA model, while the remaining 3 spectra
from the third extract were used for validation to evaluate the prediction accuracy
of the calibrated SIMCA model. The optimum number of PCs in each class was
selected on the basis of the lowest number of PCs giving minimum value of
variance.
32
4.3.1 Optimization of Solvent Extraction for FTIR-ATR
deionised water, NH4OH solutions (0.25, 0.5, 0.75, and 2.5 M), and HCl solutions
(0.05, 0.1, 0.15, and 0.25 M) on coffee wetting were evaluated at different
volumes (0.5, 1.0, and 1.5 mL). The FTIR spectra data showed that there was no
significant difference between alkaline, acid, and neutral wetted samples (data
not shown). There was no difference between adding 0.5 mL and 1.0 mL
solutions were added, probably due to the dilution effect. On the basis of the
positive preliminary experiment findings, 1.0 mL water was added during ground
coffee extraction.
The effects of water on the solvent extraction have been reported previously.
Yamamoto et al. studied the efficiency of various organic solvents for cadmium
reported that solvent at 53% (organic phase to water) was the most efficient in
maximizing the isoflavone extraction in soy food matrix (Murphy et al. 1999).
behaviours were observed among the tested solvents due to their different
physical properties (Table 3). When extraction was carried out in the presence of
water (Method #1), the solvent phase of dichloromethane was at the bottom,
33
while hexane, ethyl acetate, acetone, ethanol, and acetic acid phases were on
top (Figure 6). Three layers (solvent, water, ground coffee phases) were
solvent because they were immiscible or slightly soluble in water. The three
layers observed were likely caused by the different densities of ground coffee,
water, and solvent. However, for acetone, ethanol, and acetic acid extractions,
only two phases were observed since these solvents were miscible with water.
For coffee extracted by method #1, coffee grinds were all in one layer. On the
other hand, in the presence of organic solvent alone (Method #2), the extract
layers were hazy, and tended to contaminate with grind particulates. This may be
due to the fact that when the samples were wetted with water, the entrapped air
in the ground coffee matrices was readily displaced by the solvents, thereby
34
Hexane Extract
Dichloromethane Extract Ethyl acetate Extract
acetate, acetone, ethanol, and acetic acid (the right vial represent the extracts by
Method #1)
to evaporate on the ATR crystal to remove the solvent. The required times for
dichloromethane, and hexane had relatively short evaporation times due to their
immiscibility with water. Intermediate evaporation time was observed for ethyl
acetic acid are completely miscible with water, resulting in relatively long
evaporation times. The extended evaporation time for these solvents may not be
desirable due to the potential loss of coffee volatile compounds (Mottaleb et al.
1997) .
35
Table 4 Evaporation time of the coffee extracts
Dichloromethane extract 60 60
Hexane extract 60 60
water) and #2 (no water) are shown in Figure 7. The 3100 to 2750 cm-1 region in
the majority of spectra (except acetic acid, acetone, and ethanol extracts
obtained with extraction method #1) were typical for the fatty acid moiety of lipids
2954 cm-1) (Innawong et al. 2004). In the presence of water, the absorbance
around 3676-3028 cm-1 for acetic acid, acetone, and ethanol extracts can be
attributed to the O-H stretching band. The 1800–800 cm-1 region contained
absorbance bands due to C=O (ester, aldehydes, and ketones) stretching, C-H
36
(methylene) bending (scissoring), and C-O (esters and alcohol), CH2
information that may be important for discriminating coffee samples from different
origins.
Spectra from method #1 extracts were relatively more complex than those
were used for extraction. For instance, dichloromethane extract from method #1
resulted in many additional peaks that were absent for those from method #2,
including 1487 cm-1 (C=C, C-H deformation), 1398 cm-1 (CH3 symmetric
deformation), 1323 cm-1 (symmetric vibrations of COO- groups), and 1284 cm-1
band shape and intensity, different spectral features were observed in the 1720-
1203 and 1064-940 cm-1 regions. With method #1, water-induced swelling of the
and ethyl acetate coffee extracts. For the hexane and acetic acid extracts,
minimal spectral differences were observed between methods #1 and #2. The IR
spectra of the hexane extracts were similar to lipid (Hennessy et al. 2009)
indicating that lipids may be the main components extracted when hexane was
used as a solvent. Overall absorbance values were considerably stronger for the
acetone and ethanol extracts probably due to the contribution from water present
in the extracts. The spectra of acetic acid extracts and pure acetic acid were
similar (data not shown), indicating that acetic acid is not an effective solvent for
37
coffee extraction. On the basis of the evaporation time data and FTIR spectral
3.6 Hexane extract Enlarge region (1800-800 cm-1) 3.6 Dichloromethane extract Enlarge region (1800-800 cm-1)
3.2 3.2
2.8 2.8
Absorbance
Absorbance
2.4 2.4
No water
2.0 No water 2.0
0.0 0.0
3600 3000 2400 1800 1200 600 1800 1600 1400 1200 1000 800 3600 3000 2400 1800 1200 600 1800 1600 1400 1200 1000 800
Wavenumber, cm -1 Wavenumber, cm-1 Wavenumber, cm-1 Wavenumber, cm -1
3.6 Ethyl acetate extract Enlarge region (1800-800 cm-1) 3.6 Acetone extract Enlarge region (1800-800cm-1)
3.2 3.2
2.8 2.8
No water No water
Absorbance
Absorbance
2.4 2.4
No water No water
2.0 2.0
With water
1.6 1.6
With water
1.2 1.2
With water
0.8 With water 0.8
0.4 0.4
0.0 0.0
3600 3000 2400 1800 1200 600 1800 1600 1400 1200 1000 800 3600 3000 2400 1800 1200 600 1800 1600 1400 1200 1000 800
Wavenumber, cm-1 Wavenumber, cm-1 Wavenumber, cm -1 Wavenumber, cm -1
6.4
3.6 Ethanol extract Enlarge region (1800-800 cm-1) Acetic acid extract Enlarge region (1800-800 cm-1)
5.6
3.2
2.8 4.8
No water
2.4 4.0
Absorbance
Absorbance
No water
2.0 No water
With water 3.2
1.6 No water
2.4
1.2 With water
With water 1.6
0.8
With water
0.4 0.8
0.0 0.0
3600 3000 2400 1800 1200 600 1800 1600 1400 1200 1000 800 3600 3000 2400 1800 1200 600 1800 1600 1400 1200 1000 800
Wavenumber, cm-1 Wavenumber, cm-1 Wavenumber, cm-1 Wavenumber, cm-1
ethyl acetate, acetone, ethanol, or acetic acid using method #1 (with water) and
coffee beans from different geographic regions (Colombia, Costa Rica, Ethiopia,
and Kenya) were similar among medium roast or dark roast samples (Table 5).
38
Tukey pairwise comparison analysis (Table 6) confirmed that differences in L*
values were not significant between ground samples for dark or medium roasted
beans, implying that samples from the same degree of roast exhibited the same
lightness.
39
Table 6 Turkey method for L* value comparisons
Dark roast: MSE = 0.022908, HSD (t, αF) = 0.396; Medium roast: MSE = 0.03175,
coffee beans from various regions are presented in Figure 8. As shown, although
variances between spectra exist, the differences are subtle and data
interpretation is difficult. To extract relevant information from the data, PCA was
40
HIGH T -COLOM 2-2
0.16 Colombian
HIGH T -KENYA 1-1
HIGH T -ET HIOPIAN 1-1
HIGH T -COST A 1-1
Kenyan
Abs
Ethiopian
0.14 Costa Rican
0.12
0.1
0.08
0.06
0.04
0.02
-0
4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750
FTIR Measurement 1/cm
Figure 8 Selected FTIR spectra of dark roast coffee extract obtained with
41
Hexane Extract Dichloromethane Extract Ethyl acetate Extract Acetone Extract
Colombian Costa Rican Ethiopian Kenyan Colombian Costa Rican Ethiopian Kenyan Colombian Costa Rican Ethiopian Kenyan Colombian Costa Rican Ethiopian Kenyan
0.002 0.002 0.002 0.002
-0.001
-0.002 -0.002 -0.002
B
0.05 0.05 0.05 0.05
Absorbance
2850 1743
2920
Absorbance
0.12 0.12 0.12 0.12
Absorbance
2850
C 1550
0.08 2920 0.08 0.08 0.08
1741 1726
2850
0.04 0.04 0.04 0.04
Figure 9 PCA of FTIR data for hexane, dichloromethane, ethyl acetate, and acetone extracts of medium roast coffee.
Row A: Two-factor score plots. Row B: Loading plots of PC1. Row C: Corresponding FTIR raw spectra
42
Hexane Extract Dichloromethane Extract Ethyl acetate Extract Acetone Extract
Colombian Costa Rican Ethiopian Kenyan Colombian Costa Rican Ethiopian Kenyan Colombian Costa Rican Ethiopian Kenyan Colombian Costa Rican Ethiopian Kenyan
0.002 0.001 0.002 0.002
Dichloromethane
2nd Principal Component
0.000
0.000
A 0.000 0.000
-0.001
-0.001
-0.001 -0.001
-0.002
Absorbance
Absorbance
0.12 0.12
Absorbance
2920 1662
2850 1550
C 0.08 0.08 0.08 2850 0.08
Figure 10 PCA of FTIR data for hexane, dichloromethane, ethyl acetate, and acetone extracts of dark roast coffee. Row
A: Two-factor score plots. Row B: Loading plots of PC1. Row C: Corresponding FTIR raw spectra
43
For the medium roast coffee samples, FTIR data for dichloromethane and
which corresponded to the four countries of origin (Figure 9, row A); however,
cluster patterns were less discernible for hexane and acetone extracts. For the
dark roast samples, the PCA score plots of FTIR data for all the solvent extracts
showed clear distinctive groupings for coffee beans from the four countries of
origin (Figure 10, row A). Overall, separation distances between clusters were
greater for the dark roast samples than for the medium roast counterparts,
implying that the IR active-active components that were distinctive to the bean
origin tended to develop when the beans were roasted to a darker degree.
aroma compounds, and aroma profiles are dependent on the time and
temperature regimes applied during the roast process (Lyman et al. 2003). The
greater cluster separation for dark roast samples observed in the current study
used. The polarity index for hexane, dichloromethane, ethyl acetate, and acetone
are 0.1, 3.1, 4.4, and 5.1, respectively (Byers 2003). Thus, hexane is non-polar
and extracts only non-polar compounds from coffee. On the other hand, acetone
dichloromethane and ethyl acetate, both polar and non-polar compounds are
44
extracted. The polarity effect can be observed in the original spectra (Figures 9
and 10, row C). The spectral region from 3676-3028 cm-1 is mainly due to the O-
H stretching band from water. As shown, the absorbance intensity in this region
acetone in ascending order. This result is consistent with the polarity for these
solvents.
focused on PC1 since it explained the maximum variance existing in the dataset
(Figures 9 and 10, row B). The percent variance accounted by PC1 was also
indicated on each loading plot. Regions of each spectrum with a relatively large
loading score (>0.1) were highlighted as red dotted lines. As shown, the loading
plots for hexane extracts were markedly different than those of the other three
solvent extracts, due to the non-polar nature of hexane. The loading plots of
hexane extracts for medium and dark roasts were similar, except that
mode of fatty acid esters, was higher and wider in the medium roast compared
with the dark roast coffee (Yoshida et al. 1997). For dichloromethane extracts,
the most prominent difference in loading plots for dark and medium roast coffees
Nabedryk 1982). The medium roast coffees exhibited significant loading score
around this region, but negligible for dark roast coffees. A similar trend was
45
observed for the region around 1741-1678 cm-1 The minimal changes observed
for these spectral regions for the dark roast samples could be caused by a
decrease in protein and lipids due to the Maillard reaction and pyrolytic cleavage,
For ethyl acetate extracts, loading plots for medium and dark roast coffees
were comparable, indicating that the compounds extracted by ethyl acetate from
medium and dark roast coffees were similar, although subtle differences did exist.
The main regions that contribute to the differences between samples are 1743-
1741, 1647-1643, and 1697 cm-1. The band at 1697 cm-1 is due to isolated
1990). Garrigues et al. (Garrigues et al. 2000) and Ohnsmann et al. (Ohnsmann
et al. 2002) also utilized absorbance at 1659 and 1704 cm -1 to determine the
caffeine content in coffee and tea, respectively. In these cited studies, the C=O
bands investigated shifted to higher frequencies due to the different solvent used
clusters observed were partly caused by the different caffeine contents of among
ketones), 1655 cm-1 (C=O stretching of caffeine compounds), 1599 cm-1 (-NH
group), and 1548 cm-1 (N-H bending of peptide groups). These bands were also
detected in ethyl acetate and acetone extracts with some shifts (1701, 1651,
46
1604, and 1552 cm-1 for ethyl acetate; 1699, 1647, 1599, and 1558 cm -1 for
acetone) (Magidman 1984; Mishra & Kumar 2002). For hexane extracts, the most
prominent spectral difference between the medium and dark roast coffees is that
the latter showed a stronger overall absorbance, implying that more lipids (1600-
1700 cm-1) and fatty acid esters (1700-1800 cm-1) were being extracted from the
dependent, the quality and sensory properties of the resulting coffees can vary
taste and aroma, and carries citrus taste. In comparison, dark roast coffee has a
heavier sweet taste, with a lingering aftertaste of chocolate (Schenker et al. 2002;
corresponding to dark coffees (right clusters) and medium coffees (left clusters)
from the four origins. The loading plots for dichloromethane extracts showed that
all coffee samples, except the Columbian coffee, exhibited strong loading scores
at 2920, 2850, and 1743 cm-1 due to CH2 asymmetrical stretching of methyl
47
aliphatic esters (Hennessy et al. 2009; Wang et al. 2009). For the Colombian
coffee, the bands that correspond to significant loading scores at 1550, 1510,
and 1481 cm-1 can be attributed to N-H bending of peptide groups, C=N
For ethyl acetate extracts, the loading plots revealed that spectral regions
that contributed to cluster separation were mainly at 2850-2920 cm-1 due to CH2
vibrations and C=N stretching (Paradkar & Irudayaraj 2002). For coffee, this
cm-1) (Bellamy 1975; Keller 1986; Socrates 1994). Absorbance in the 2850-2920
(1725-1705 cm-1), aromatic acids (1700-1680 cm-1), and aliphatic acids (1714-
1705 cm-1), but a decrease in caffeine content (1700-1692 cm-1, and 1647-1641
cm-1) (Lyman et al. 2003; Movasaghi et al. 2008; Wang et al. 2009). Others have
also observed decreases in the amount of lipids (around 1736, 1740, 1745, and
48
cm-1), and lipids/proteins (2935-2847 cm-1) (Lyman et al. 2003; Movasaghi et al.
49
Colombian Costa Rican Ethiopian Kenyan
Dark roast Medium roast Dark roast Medium roast Dark roast Medium roast Dark roast Medium roast
0.002 0.002 0.002 0.002
2nd Principal Component
A
0.000 0.000 0.000 0.000
Absorbance
0.12 0.12
Absorbance
0.12
Absorbance
829
C 1695
1510 1678
0.08 0.08 0.08 0.08
1550 860
0.04 0.04 0.04 0.04
Figure 11 PCA of FTIR data for dichloromethane extracts of coffee (from the same origin) with two degrees of roast. Row
A: Two factor score plots. Row B: Loading plots of PC1. Row C: Corresponding FTIR raw spectra
50
Colombian Costa Rican Ethiopian Kenyan
Dark roast Medium roast Dark roast Medium roast Dark roast Medium roast Dark roast medium roast
0.002 0.002 0.002 0.002
2nd Principal Component
1647 1674
1674 1674
0.20 0.20 1701 0.20 0.20 1701 1647
1674
1236
Absorbance
Absorbance
Absorbance
Absorbance
Figure 12 PCA of FTIR data for ethyl acetate extracts of coffee (from the same origin) with two degrees of roast. Row A:
Two factor score plots. Row B: Loading plots of PC1. Row C: Corresponding FTIR raw spectra
51
4.3.5 SIMCA Analysis
roast, SIMCA classification was employed to predict the origin and degree of
Table 7 shows the results of the prediction performance for coffee from
different origins based on SIMCA models at the 5% significance level. Except for
the dichloromethane extract for the Ethiopian medium roast sample, all other
samples were correctly assigned to the country of origin during model validation.
Similar validation results were obtained for the prediction degree of roast within
each coffee (Table 8). Overall, ethyl acetate is a more optimal solvent for the
common solvent used for decaffeinating coffee and tea leaves (Dusseldorp et al.
52
Table 8 SIMCA classification results for coffees according to degree of roast
Dark Medium
Colombia 100 67
analysis methodologies may be useful for the coffee industry as a rapid and
degree of roast. Also, the methods may be useful for routine quality evaluation
coffee varieties and study using bigger sample size are necessary to improve the
53
5 EFFECTS OF DIFFERENT TIME-TEMPERATURE PROFILES ON
5.1 Introduction
Green coffee beans provide neither the characteristic aroma nor the taste of
a cup of coffee. To reveal their flavour, green coffee beans need to be roasted.
Roasting is one of the most important steps in coffee processing that leads to the
development of the desired aroma, taste, and color of the final brewed product. In
in the coffee beans (Schenker 2000; Schenker et al. 2002; Baggenstoss et al.
2008).
The time and temperature conditions applied during roasting have a major
impact on the physical and chemical properties of roasted coffee beans. Geiger
et al. reported that CO2, a by-product formed due to Strecker reactions and the
high-temperature-short-time process (260oC, 170 s), while the CO2 formed was
employed (Geiger et al. 2005). Schenker et al. found that roasting process that
54
led to beans of lower density, higher volume, less roast loss, and lower moisture
al. 2008). Lyman et al. roasted green coffee beans under various process
conditions to study the effect of roasting on brewed coffee (Lyman et al. 2003).
Using a medium roast process (6.5 min to the onset of the first crack and 1.0 min
to the onset of the second crack), Lyman et al. observed that coffee of balanced
taste and aroma with citrus flavour was produced. However, using the so-called
“sweated process” (4.5 min to the first crack and 6.5 min to the second crack),
coffee beans of non-uniform bean color with “sour, grassy, and underdeveloped”
were resulted. In comparison, the “baked process” (11 min to the first crack and
18 min to the second crack) produced coffees that were “flat, woody with low
brightness and acidity” (Lyman et al. 2003). Based on the these observations,
one can conclude that the quality of roasted coffee does not solely depend on the
physical parameters at the start and end point of roasting, but rather it is
process.
methodologies, such as PCA, PCR, PLS, ANN have been successfully applied in
screening of defective green coffee beans, and shelf-life study (Eliane Nabedryk
1982; Keller 1986; Socrates 1994; Dovbeshko 1997; Yoshida et al. 1997;
55
Fukuyama 1999; Hennessy et al. 2009). Although gas chromatography-mass
instruments (electronic noses and tongues) have been used for studying the
aroma compounds in roasted coffee (Rahn & Konig 1978; Parliment & Stahl 1995;
Kantor & Fekete 2006), analyses involving these techniques are time-consuming
simple technique which is rapid and provides an overall infrared fingerprint of the
cm-1 region of the IR spectrum of coffee brews. The carbonyl stretching region
esters/lactones, esters, aldehydes, ketones, and acids (Lyman et al. 2003). In our
study are to: (1) develop the understanding of the effects of time-temperature
coffees roasted to the same stage by different roasting profiles using FTIR-ATR
technique.
56
5.2 Materials and Methods
ethanol from Greenfield Ethanol Inc. (Brampton, Canada), and sodium hydroxide
(Arabica) from Brazil were donated by Mother Parkers Tea & Coffee Inc.
Green coffee beans (45 g) were roasted in a fluidized bed hot air roaster
(Fresh Roast SR 500, Fresh Beans Inc., Park City, UT). Four isothermal roasting
programs were used for roasting (Table 9). Coffee beans were collected at six
quenched. The roasted bean samples were stored in hermetic glass bottles in the
57
Table 9 Time Taken to Achieve Different Stages of Roasting at Four Different
Roasted coffee beans were ground using a coffee grinder (Bodum Antigua
Electric Burr Grinder, Bodum, Inc., Copenhagen, Denmark) at the medium grind
setting. The colour of the ground coffee was measured in the L*, a*, b* system
Inc., Osaka, Japan) in the reflectance mode. Before analysis, the instrument was
carried out using oven dehydration method according to the Swiss Food Manual
58
(SWFOH 1973). Samples of roasted beans were ground finely, and then dried at
5.2.5 pH Value
A 2.00 g ground coffee was accurately weighed into a 200 mL glass bottle,
and 100 mL of deionized water was added in. The glass bottle was boiled for 10
min. Then, 50 mL of the filtered extract was used for pH value determination with
bottle, and 75 mL 80% ethanol was added to wet the sample. The glass bottle
was shaken for 16 h under magnetic stirring. After that, 50 mL of the filtered
extract was titrated against 0.1 N NaOH solution (Horwitz 2000). Measurements
After grinding, coffee grounds were extracted with ethyl acetate following
the extraction procedure: 0.2500 g of ground coffee was accurately weighed into
a glass vial, and 1 mL of deionized water was added to wet the sample. The
glass vial was shaken for 1 min; 1 mL of ethyl acetate was added, and the
mixture was shaken for an additional 5 min. The organic phase was used for
ATR-FTIR analysis in the region of 600 to 4000 cm-1 at 4 cm-1 resolution (Wang
59
5.2.8 Chemometric Analysis
the data structure. Second derivative and mean-center were applied to FTIR
Coffee bean samples were cut perpendicular to the crevice to expose the
internal bean structure. The bean samples were coated with 20 nm of gold in a
sputter coater (Model K550, Emitech, Ashford, Kent, England). The pore
Roasting causes the buildup of pressure within the coffee bean due to the
formation of steam and other gases. The increased internal pressure causes the
bean to expand and crack, resulting in a phenomenon known as the “first crack”.
60
and generate a large amount of CO2, with concomitant degradation of
carbohydrates and amino acids. When the pressure buildup exceeds the strength
of the cellulosic cell wall, rapid popping of coffee bean occurs – a roasting event
are often used to evaluate the progress of roast processing of coffee beans.
Moisture content, %
9
50 (ii)
Accordingly, these events (i)were chosen 8as the reference sampling points in the
40 present study. 7
6
30 In Figure 13A, the evolution of color, moisture content, pH value, and
5
0.80
A
5.6 9
50
(i)
0.60 (ii)
8 210 C
5.4 220 C
Moisture content, %
Lightness, L*
10 3
6.0 1.20
1.00 (iv)
5.8
Titratable acidity, g/L
0.80
5.6
pH value
5.0 0.00
61
3
1.20
1.00 (iv)
Moisture content, %
40 7 220 C
Lightness, L*
10
0.00
3
-2 1 4 7 10 13 16 19 -2 1 4 7 10 13 16 19
6.0
Time, min Time, min
1.20 (iv)
5.8 (iii)
1.00
5.6
5.4
0.60
Stage of roasting
5.2 0.40 Stage of roasting
5.0 0.20
4.8 0.00
-2 1 4 7 10 13 16 19 -2 1 4 7 10 13 16 19
Time, min Time, min
of coffee beans processed to different roast stages (A). The same data are
coffee bean during roasting (Illy & Viani 1995; Eggers & Pietsch 2001) caused by
(Massini et al. 1990; Parliment Thomas 2000). Lightness (L*) is often used as a
measurement of the degree of roast (e.g., light, medium, and dark), which is
directly related to the roasting time and temperature (Sivetz 1991; Illy & Viani
bean samples achieved a similar degree of roast (i.e., medium roast), with L*
62
values ranging between 25 and 28, regardless of the roast temperatures used. At
beans attained dark roast. This result indicates that the first and second cracks
correlated well with lightness of the roasted coffee, and these milestones could
be used as one of the parameters to evaluate the degree of roast in coffee beans.
During the first phase of roasting (before the second crack), variation of
lightness between beans was observed. However, when the beans were roasted
Figure 13B(i), the slopes for L* value versus roast time plots decreased when the
change in slope is more prominent for beans roasted at lower temperatures (e.g.,
moisture content during roasting. During the early phase of roasting (up to the
the coffee beans. The rapid loss in moisture during the initial phase of roasting
increased above the boiling point of water. From the end-of-first-crack to the
63
degradation of chlorogenic acids, other organic acids, and lipids (Yeretzian et al.
observed could be caused by the further rupturing of cell walls, allowing the
final moisture content was observed for the final products regardless the roaster
contents for the former may be attributed to the limited diffusion of water from the
bean to the surrounding air due to the short processing time involved.
formation of formic, acetic, glycolic, and lactic acids as the coffee beans were
attributed to the destruction of organic acids formed and those that were present
initially (citric acid, malic acid, and chlorogenic acids), as the coffee beans were
taken to darker roasts (Ginz et al. 2000). Before the start-of-second-crack, the pH
64
value was lower for samples roasted at higher temperature as compared to those
roasted at lower temperatures. This trend is likely due to faster rate of the
process continued to the start-of-second-crack, the trend was reversed due to the
greater destruction of formic and acetic acids at higher temperatures (Ginz et al.
2000).
between the pH value and the perceived acidity of coffee (Sivetz & Desrosier
1979; Griffin & Blauch 1999). However, some recent findings on perception
acid molecules are important for acid perception Therefore, titratable acidity in
coffee brews could be a more reliable indicator for correlating the coffee acidity
than the pH value (Voilley et al. 1981; Brollo et al. 2008). As shown in Figures
13A(iv) and 13B(iv), a rapid increase of titratable acidity was observed as green
coffee beans were roasted to the end-of-first-crack (medium roast). This change
maximum level (Clarke & Macrae 1988). Consistent with the pH value, further
due to the destruction of organic acids (e.g., citric, malic, lactic, pyruvic, and
acetic acids) (Clarke 1986). In general, medium-roast Arabica coffee brews have
65
a pH value ranging between 4.9 and 5.2, which is in agreement with the result
from the present studies (pH 5.2, 5.16, 5.1, and 5.14 for 210, 220, 230, and
240°C, respectively) (Clarke & Macrae 1988). These observations suggested that
by using different roast temperature and time profiles, the titratable acidity in
roast coffees could be manipulated. For example, the maximum titratable acidity
can be obtained by using 210oC roast temperature before second crack started,
compositional changes in coffee beans. These changes are both time and
produced more soluble solids, less degradation of chlorogenic acids, lower loss
of volatiles, less burnt flavour, larger volume increase, larger CO2 desorption, and
In the present study, coffee beans were processed at 210, 220, 230, or
240oC to achieve a similar degree of roast (all dark roast), based on the L* value.
Bean samples were collected at six roast stages, ground into powder, extracted
in solvent, and then analyzed with FTIR spectroscopy. Typical FTIR spectra of
66
dataset. As shown in Figure 14 (column A), for all the temperatures tested, the
score plots displayed clusters that were separated according to different stages
of roast. There is a clear trend for the clusters to move upwards along the PC-2
axis as the roasting progressed through different stages. The clusters for green
coffee were separated far from the other clusters, indicating that the chemical
stages when low roast temperatures were used (e.g., 210 oC). However, at higher
temperature (e.g., 240oC), the clusters had a tendency to spread along the PC1
axis as the roasting process progressed. Further analysis of PC1 loading plots
(data not shown) revealed that frequencies that contribute to the spectral
difference for beans roasted at 210 and 240oC occurred at around 2920-2850
contents had occurred during roasting, especially the lipids. This is consistent
with the observation that during the roasting experiment, spots of oil were
observed on the surface of beans that were roasted at 240 oC, but not those
have increased the rate of oil diffusion from the bean core to the surface
samples, the loading plots for PC2 were also inspected (Figure14, Column B).
67
The percent variance accounted by PC2 was indicated on each loading plot.
Regions of spectrum with large loading score (>0.1 and < -0.1) mainly appeared
at 2920, 2850, 1739, and 1660 cm-1, which are due to CH2 asymmetrical
and fatty acids, respectively (Shetty 2006; Hennessy et al. 2009). For coffees
roasted at 220 and 230°C, more absorbance with large loading score (>0.1 and <
-0.1) were observed than those roasted at 210 and 240°C, especially at 1741 cm-
1
(fatty acid esters), 1718-1707 cm-1 (ketones), 1697 cm-1 (aromatic acids), and
1514 cm-1 (amino groups). These compounds are important in determining the
overall coffee organoleptic qualities. For example, esters provide softer and
woody, cucumber, cooked fruit, and nuts. On the other hand, acids are important
(Ginz et al. 2000; Lyman et al. 2003). Silwar and Lüllmann reported that the “real”
flavour of roasted coffee appeared at 220-230oC. Beyond this point, the flavor
processed at 250 to 260oC (Silwar & Lüllmann 1993). For coffees roasted at
210oC, some key compounds that contribute to aroma such as furans, pyrazines,
strecker aldehydes, and 2- and 3-methylbutanal might have not been fully
68
A B C
Green coffee beans
start-of-first-crack
PC 2 Loading (19.2%)
0.005 0.25 0.20
Absorbance
210 C
0.001 48s-after-second-crack 0.12
0.05 2850 1514
-0.001 0.08
-0.05
-0.003 0.04
end-of-first-crack 1660
48s-after-first-crack 1697
0.003 0.16 2920 1707
start-of-second-crack 0.15 1739
end-of-second-crack
Absorbance
1741
0.001 0.12
220 C
48s-after-second-crack 2850
0.05 1514
-0.001 0.08
-0.05
-0.003 0.04
48s-after-first-crack 1660
0.003 start-of-second-crack 0.16 1697
end-of-second-crack 0.15 2920 1707
1739
Absorbance
48s-after-second-crack
230 C
end-of-first-crack 1660
0.003 48s-after-first-crack 0.16 2920
start-of-second-crack 0.15
2850
Absorbance
240 C
end-of-second-crack 1739
0.001 0.12
48s-after-second-crack
0.05 2839
-0.001 0.08 1514
-0.05
-0.003 0.04
Figure14 PCA analysis for coffees during roasting. Column A: Two-factor score plots. Column B: Loading plots of PC2.
69
The IR spectra at 230oC were overlaid to examine the differences at
different roast stages (Figure 15). Compounds that accounted for the observed
cm-1), and caffeine (1650-1600 cm-1) (Bellamy 1975; Keller 1986; Socrates 1994;
Briandet et al. 1996b; Hennessy et al. 2009). As shown in Figure 15, the spectral
cm-1), and caffeine (1650-1600 cm-1) decreased from the start-of-first-crack to the
1740 cm-1) and aldehydes (1739-1724 cm-1) gradually increased from the start-
second-crack.
70
0.20 1725-1705 start-of-first-crack
start-of-second-crack
0.12 end-of-second-crack
48s-after-second-crack
0.08 1550
1780-1762
0.04
0.00
2950 2900 2850 2800 1800 1775 1750 1725 1700 1675 1650 1625 1600 1575 1550 1525 1500
Wavenumber, cm-1
Figure15 The expanded 2910-2850 cm-1, and 1800-1500 cm-1 regions of the spectra of coffee roasted at 230oC
71
5.3.3 Effects of roast temperature on changes in coffee
Overall, clusters for the score plots were well separated according to
different roasting temperatures (Figure 16, column A). The separation distance
between 220 and 230oC tended to be closer during the first three stages of roast,
indicating that the IR-active components are similar in the coffee beans roasted
at these two temperatures. From the loading plots (Figure 16, column B), it is
from those of the other five stages, in that the former exhibited less number of
bands with large loading score, which could be due to the fewer compounds
extracted during the short process time (Lyman et al. 2003). Loading plots for
different temperatures were similar. The main regions that contributed to the
1726, 1699-1701, and 1676 cm-1, due to aldehydes/ketones, aromatic acids, and
lipids, respectively (Bellamy 1975; Keller 1986; Socrates 1994). Other spectral
stretching band of fatty acids (Shetty 2006), 1650 cm-1 due to Amide I of protein
(Dovbeshko 1997), 1550 cm-1 from Amide II of proteins (Fukuyama 1999), and
1514 cm-1 caused by N=C stretching of amino groups (Barua et al. 2008).
72
A B C
210 C-1 220 C-1 230 C-1 240 C-1 PC 1 Loading (47.5%)
0.005 0.15 0.20
Absorbance
0.12 1741
0.001 -0.05 2850
0.08
-0.001 -0.15
0.04
210 C-2 220 C-2 230 C-2 240 C-2 PC 1 Loading (68.4%)
0.005 0.15 0.20 1514
1691
2nd Principal Component
1660
end-of-first-crack
0.16
0.003 0.05 1650
Absorbance
0.12
1556
0.001 -0.05
0.08 1550
1541
-0.001 -0.15
0.04
3649
210 C-3 220 C-3 230 C-3 240 C-3 PC 1 Loading (51.0%) 1514
0.005 0.15 0.20 1689-1691
1676
1699-1701
2nd Principal Component
1660
48s-after-first-crack
0.16 1650
0.003 0.05 1566
Absorbance
1724-1726 1556
0.12
0.001 -0.05 1541
0.08
-0.001 -0.15
0.04 3649
210 C-4 220 C-4 230 C-4 240 C-4 PC 1 Loading (47.5%)
0.005 0.15 0.20
2nd Principal Component
1670
start-of-second-crack
0.16
0.003 0.05 2920 1724
Absorbance
0.12 1741
0.001 -0.05 2850 1514
0.08
-0.001 -0.15
0.04
0.16 1724
0.003 0.05 2920 1514
Absorbance
-0.001 -0.15
0.04
210 C-6 220 C-6 230 C-6 240 C-6 PC 1 Loading (45.0%)
0.005 0.15 0.20 1670
2nd Principal Component
48s-after-second-crack
1689
0.16 1724
0.003 0.05 2920
Absorbance
0.12 1741
0.001 -0.05 2850 1514
0.08
-0.001 -0.15
0.04
Figure16 PCA analysis for coffees collected at the same sampling point. Row A:
73
At the start-of-second-crack and end-of-second-crack, the separation
samples processed at higher temperatures (230 and 240 oC). These results imply
that the second crack is an important milestone during coffee roasting, at which
employed.
When the beans were heated to the start-of-first-crack, a few pores started to
roasted to the second crack, further expansion of the pores is evident from the
the pores. Furthermore, the pores were more polyhedral in shape than those
appeared in earlier roast stages, suggesting that there was an increased internal
74
pore pressure that causes the pores to compress against each others, likely due
to the evolution of carbon dioxide. The carbon dioxide build up may have also
resulted in ruptured walls exhibited for some pores. Further heating to 48 s-after-
second-crack resulted in morphologies that were less uniform than the previous
stages, possibly due to the artefacts caused by the disruption of brittle cell wall
processed to the last two roasting stages revealed the presence of droplets on
the surface of the pore walls. The droplets may be attributable to the coalesced
beans of higher porous structure in the bean cell tissues as compared to low-
to result in higher extraction yield during solvent extraction (Pittia et al. 2001).
However, at the magnification level employed during the SEM analysis and
roasting conditions used, no correlation can be made between the pore size and
roasting temperature. The lack of correlation could be due to the sample cutting
procedure involved, which does not guarantee the sectioning through the
75
Figure 17 SEM micrographs of internal texture for coffee beans collected at different stages of roast. The temperatures
76
In summary, this study showed that coffee beans processed to the same
extent of roast (as determined from bean lightness and roast cracking milestones)
for studying the effect of roasting conditions on IR-active compounds. The FTIR-
chemometric technique adopted in this study could serve as a rapid tool for
77
6 Conclusions and Future Works
This research studied the physicochemical changes that took place during
roaster.
samples from different geographical regions and roast degrees, using solvent
a mixture of equal volume of the solvent and water resulted in an optimal extract
PCA analysis of the FTIR spectra of extracts prepared from solvents of different
coffees. From the FTIR spectra, we observed that roasting coffee from medium
and aliphatic acids (1714-1705 cm-1), but a decrease in caffeine content (1700-
1692 cm-1, and 1647-1641 cm-1), lipids (around 1736, 1740, 1745, and 1750 cm-
1
), and polysaccharides and hemicelluloses (1739 cm-1). The SIMCA models
developed here may be useful for the coffee industry as a rapid and accurate tool
for classification of coffee according to origin and degree of roast. Also, the
78
methods may be useful for routine quality evaluation and complement
sensorial/cupping procedures.
of roast, Brazilian beans were roasted at different temperatures (210, 220, 230,
and 240oC) until dark roast products were achieved. Coffee beans samples,
collected at different milestones during the thermal process, were analyzed for
pH value, titratable acidity, moisture content, and color lightness. When roasted
higher titratable acidity, higher porous structure in the bean cell tissues, and also
produced more aldehydes, ketones, aliphatic acids, aromatic acids, and caffeine
analysis of ethyl acetate extract of roasted coffees showed that for all the
temperatures tested, the score plots displayed clusters that were separated
temperatures. From this study, we can conclude that coffee beans processed to
the same extent of roast (as determined from bean lightness and roast cracking
necessarily have the same physical and chemical properties. FTIR-ATR analysis
79
chemometric technique potentially can be used for detecting process deviation in
production roasters.
chemometric, FTIR and other analytical methodologies, the project has achieved
changes that took place in various coffee beans. While there is a significant gain
in knowledge from this project, there are still a number of unanswered questions
that are yet to be answered. The followings are several topics that are worth
further investigation:
After roasting, coffee beans are quenched to remove the residual heat
quickly. This process can trap significant amount of CO2 in the bean,
thereby lengthens the required time for CO2 degassing. This is a critical
agitation will remove the residual heat from the coffee beans rapidly due to
the latent heat of vaporization of water. The humidified air may increase
part of the roasting regime towards the end of the roast cycle before
80
diffusivity of CO2, potentially shortening the duration of the degassing step.
involving more coffee varieties and larger sample size will improve the
Due to the time constraint, sensory studies were not conducted in this
81
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