Roasting Effectson Nutritionaland Antinutritional Compoundsin Coffee

4
Roasting Effects on Nutritional and

Antinutritional Compounds in Coffee
Jeane Santos da Rosa, Otniel Freitas-Silva, Ronoel Luiz

de Oliveira Godoy, and Claudia Moraes de Rezende
CONTENTS
4.1 Introduction ...................................................................................................... 48
4.2 Background ...................................................................................................... 48
4.3 Coffee Production and Consumption ............................................................... 48
4.4 Coffee Quality from Farm to Cup ................................................................... 49
4.4.1 Wet Method ......................................................................................... 50
4.4.2 Semidry or Pulped Natural Method: Pulped Coffee........................... 50
4.4.3 Dry or Natural Method ........................................................................ 50
4.5 Coffee Roasting ................................................................................................ 52
4.6 Roasting Techniques and Their Control .......................................................... 53
4.7 Roast Standards X Regional Roast Preferences............................................... 53
4.7.1 Is the Dark Roast a Tool to Mask the Poor Quality of the Grain? ...... 54
4.8 Coffee Aroma Complexity ............................................................................... 56
4.8.1 How Maillard Reactions and Caramelization Govern Coffee
Flavors? ................................................................................................ 56
4.8.2 Melanoidins ......................................................................................... 58
4.8.3 Caramelization and Torrefacto Roasting ............................................. 58
4.8.4 Coffee Aroma Overview ..................................................................... 59
4.9 Physical Changes during Coffee Bean Roasting .............................................60
4.10 Coffee Roasting: Bioactive and Antinutritional Substances ............................60
4.10.1 General Composition of Green Coffee ................................................60
4.10.2 Chemical Modifications on Roasting: Degradation
and Formation of Bioactive Molecules................................................64
4.10.3 Possible Formation of Toxic By-Products ........................................... 65
4.11 Coffee Composition Parameters and Health Claims ....................................... 68
4.12 Concluding Remarks ........................................................................................ 69
Acknowledgments...................................................................................................... 69
References .................................................................................................................. 70
47
48 Food Processing Technologies
4.1 Introduction
Coffee plays an important economic and social role, worldwide. The global accep-
tance of coffee as a drink and commodity can be demonstrated not only in the number
of consumers but even in water quality studies, where caffeine has been considered
an anthropogenic chemical marker and its concentration has been associated with
population density (Buerge et al., 2003). Moreover, nowadays coffee is no longer seen
just as a stimulant, due to the caffeine content, but is also considered as a bever-
age with important antioxidant properties due the bioactive compounds it contains
(Liu and Kitts, 2011).
A cup of coffee harbors a complexity of aromas and flavors. Much of these are a
result of extensive technology employed from the planting, through to the process-
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ing, storing, roasting, and even to the grinding of the roasted grains (ABIC, 2009).
Technology is employed in coffee processing to transform the cherry coffee, the fruit,
into a dried bean (a seed in fact). The roasting process, however, is responsible for the
transformation of the coffee bean infusion into a palatable beverage (ICO, 2013a).
4.2 Background
Coffee plant belongs to the family of Rubiaceae, Coffea genus, which includes more
than 100 species; however, from these, only two species are usually marketed: Coffea
arabica (Arabica) and Coffea canephora (Robusta). Arabica has a distinct sweet and
floral/fruity flavor, and generally is cultivated on mountain slopes. Robusta is more
astringent, bitter, and has strong cocoa flavors; it grows at lower altitudes (easier for
mechanized production). Robusta has twice the caffeine content of Arabica, is less
acidic, and is commonly used in instant coffee. There are also differences in the
environmental and edaphoclimatic conditions needed (directly related to altitudes),
methods of processing, and drying between Arabica and Robusta species (Clifford
and Wilson, 1985; ABIC, 2009; Alves et al., 2009; Cagliani et al., 2013; ICO, 2013a).
Despite the large number of coffee species, Arabica is the only one that can be self-
pollinated and corresponds to about 70% of world coffee production. The Arabica
varieties Typica and Bourbon are the main precursors of other strains and cultivars
such as Mundo Novo (Brazil), Caturra (Brazil, Colombia), Tico (Central America),
and many others (ICO, 2013a). Robusta and Conillon (the latter mostly in Brazil) are
the two most important varieties of C. canephora, but Robusta now appears as the
common name of the species (ABIC, 2009; SCAA, 2009).
4.3 Coffee Production and Consumption

The world green coffee production (in bags × 1000) is separated by country and listed
in Table 4.1 (ICO, 2013b). These numbers put the current Brazilian production at
about 35% of the worldwide coffee production that was about 145 million bags in
2012 (Abad-Vergara, 2011).
Coffee remains the world’s second largest commodity and is only surpassed by oil
exports (Grigg, 2002; Mander and Liu, 2010). The global flow of coffee is basically
Roasting Effects on Nutritional and Antinutritional Compounds in Coffee 49
TABLE 4.1
World Coffee Production by Country (Five Largest
Producers, Sacks ×1000)
Country 2010/2011 2011/2012 2012/2013
Brazil 48,095 43,484 50,826
Vietnam 19,467 24,058 22,000
Indonesia 9129 8620 11,250
Colombia 8523 7653 8000
Ethiopia 7500 6798 8100
Source: Adapted from ICO, International Coffee Organization.
2013c. Proposed Framework for a Global System to
Improve Coffee Quality. http://www.ico.org/docu-

ments/ico-acpcquality.pdf (accessed June 28, 2013).
from the south (tropics), where it is produced, to the north where it is consumed, espe-
cially in the developed countries. Although climate helps this geographic distribution,
economics also helps to dictate this rule because countries in the north receive coffee,
process it, and reexport it (Daviron and Ponte, 2005; ICAFEBR, 2013).
4.4 Coffee Quality from Farm to Cup

Figure 4.1a shows the ripening stages of a coffee fruit from early green to overripe; in
this latter stage, the fruit has probably fermented before harvest. Coffee bean quality
depends upon the environment as climatic diversity provides variations in the acid-
ity, body, sweetness, and aroma of coffee. As an example, the differential flowering
times on the same plant produce ripe and unripe fruits at harvest time. This occurs
as a physiological response of plants to water stress and temperature variation. Green
fruits do not produce good quality coffee (ABIC, 2009; ICO, 2013c). Therefore,
the general quality of the roasted grain is the sum of climates and soil associated
with different crop management systems, harvest type and time, cherry quality and
(a) (c)
Skin
Pulp
Parchment
(b) Silverskin
Bean
FIGURE 4.1 Coffee cherry to coffee bean. (a) The physical changes in the fruit during ripening.
(b) Result of field processing. (c) Structure of a coffee cherry. (a and b: Reprinted with permission
from Sweet Maria’s Home Coffee Roasting.)
processing, bean storage, its transportation, and finally the roasting process. Thus,
coffee quality starts at the farm and the bean health (Camargo, 2010).
Figure 4.1b shows the changes in the coffee fruit till it becomes a dried bean. The
importance of coffee cherry processing is in the huge transformation that discards
80%–90% of the fruit mostly in the form of pulp and skin (Boot, 2007). Figure 4.1c
shows a schematic coffee fruit (cherry coffee). The red skin and the thin pulpy flesh
beneath it are together called “pulp.” The mucilage in the green beans is in a rigid
form and suffers a breakdown as the fruit begins to ripen, transforming it into an
insoluble hydrogel, rich in sugars. Under the mucilage there is the parchment, a highly
resistant coating that is difficult to remove and beneath it, covering the beans, there
is a thin membrane named the silverskin (Braham and Bressani, 1979). Usually, a
coffee cherry contains two seeds (a dicotyledon), but it may contain only one round
bean (a monocotyledon); these are known as peaberry seeds which are individual
growths and, technically, mutants. The name peaberry comes from the pea shape of
the seed, and in Brazil, this seed is called a moca bean (Carvalho et al., 1983; Clarke
and Macrae, 1985a; Eira et al., 2006).
After the coffee cherries have been picked, they have to undergo several processing
steps. There are three methods (with some variants) used to remove the outer parts
of the fruit that lead to the dry coffee bean. Figure 4.2 shows the principal steps of
these methods.
4.4.1 Wet Method

This method is used to produce special coffees. It is more costly but produces a better
selection of ripe and perfect fruits. The coffee produced is more aromatic and has less
bitterness (Santos et al., 2009). The main disadvantage of the wet process is the waste
disposal and environmental problems because the wastewater has a high organic load
and acidity (Murthy and Madhava, 2012).
4.4.2 Semidry or Pulped Natural Method: Pulped Coffee

This method produces less acidic coffee and with more body (body is the sensorial
attribute of flavor persistence in the mouth and it is related to viscosity). The semidry
process also has the eco-friendly advantage of using little water (Duarte et al., 2010).
4.4.3 Dry or Natural Method

The dry method is the oldest, simplest, and the most used method, worldwide. Nearly
4 weeks are required for cherries to be dried to about 12% of humidity. In this method,
the migration of mucilage flavor and loss of natural volatile substances can occur,
leading to a less aromatic coffee (Cuellar, 2007).
In general, the quality criteria of beans are based on a combination of the number
and type of defect in the beans (known as the Brazil/New York method—MAPA,
2003). In Table 4.2, the origins of the principal defects are listed. Coffee defects
can be divided into extrinsic defects that are related to foreign matter with origin
in the harvesting procedures (stones, sticks, and clods) and intrinsic defects, associ-
ated to bean health and maturity. The major defects in coffee can be called BGS
(PVA in Brazil), due to defective black, green, and/or sour grains (Farah et al., 2006;
Coffee processing
Wet or washed method
Wash-cherries are Separation Pulp removal Beans

Sun drying Mechanical
submerged in a bad or unripe mechanic friction fermentation
up 3 weeks hulling
water bath beans float up 36 hours
Semidry method
Cherris selection Mechanic Driving-beans still Mechanical

with water pulp removal with mucilage hulling
Dry method
Usually manual Drying-whole Turn over with

separation of cherries for rakes to prevent Mechanical
defective beans about 1 month fermentation hulling
Roasting Effects on Nutritional and Antinutritional Compounds in Coffee
FIGURE 4.2 Scheme of coffee cherry processing methods.

51
TABLE 4.2
Description of Some Coffee Defects
Black Delayed Harvest or Fruit on the Ground
Green Immature grain
Crushed Drying misguided or bad-hulling machine
Withered Caused by bad weather or genetic/physiological disorders
Sour Brown color shades, due to fermentation processes
CBB Grain damaged by the coffee berry borer (parasite of the coffee plantations)
Shell Intern empty grain. Caused by genetic/physiological disorders
Stinker Very unpleasant smell caused by microorganism attack or
cross-contamination
Black–green Unripe coffee bean with black–green color. Weather variations producing
immature beans and fermentation
Source: Adapted from MAPA, Ministry of Agriculture, Brazil. 2003. Technical Regulation of
Identity and Quality Rating for Coffee Benefited Raw Grain. Normative Instruction
008/2003. http://extranet.agricultura.gov.br/sislegisconsulta/consultarLegislacao.do?
operacao=visualizar&id=3476 (accessed May 25, 2013).
TABLE 4.3
Official Brazilian Terminology for Quality/Sensorial Rating of Arabica Coffee
Cup Quality Drink Sensorial Characteristics
Strictly soft Coffee with all flavor requirements from soft quality but more pronounced
Soft Coffee with pleasant mild flavor and sweet notes
Softish Coffee with mildly sweet and soft flavor, but without astringency or
roughness of taste
Hard Coffee with astringency and roughness of taste, but without strange flavors
Rioysh Coffee with some strange flavors like the penetrating odor of iodoform
Rio Coffee with pronounced strange flavors of Rioysh quality
Rio zone Coffee with very pronounced strange flavor similar to phenic acid or
iodoform. Repugnant to taste
Source: Adapted from MAPA, Ministry of Agriculture, Brazil. 2003. Technical Regulation
of Identity and Quality Rating for Coffee Benefited Raw Grain. Normative Instruction
008/2003. http://extranet.agricultura.gov.br/sislegisconsulta/consultarLegislacao.do?
operacao=visualizar&id=3476 (accessed May 25, 2013); Farah, A. et al. 2006. Food
Chem. 98: 373–380.
Franca et al., 2005; Toci and Farah, 2008; Bandeira et al., 2009). To avoid beverage
depreciation, the Brazilian government also created its own scale of cup quality that
is listed in Table 4.3 (MAPA, 2003; Farah et al., 2006).
4.5 Coffee Roasting

Coffee roasting is an operation of extreme importance to develop the specific senso-
rial properties which define a palatable beverage (Illy and Viani, 1995; Hernández
et al., 2008). Coffee roasting, from a food processing point of view, consists of a trans-
fer of mass, triggered by heating and consequently endothermic and exothermic reac-
tions (Anderson et al., 2003). Figure 4.3a shows a schematic roasting process from the
perspective of the coffee bean, based on the works of Clarke and Vitzthum (2001).
The application of heat on the beans generates a temperature field; it increases the
pressure and causes a flow of moisture and heated gases inside the beans (Hernández
et al., 2008). As the heat increases, the bean volume increases and there are subse-
quent changes in its inner structure.
The increase of the bean size, the number and size of pores, internal cavities, and
the decrease in weight and density are due to the amount of steam and CO2 released
in this process. The amount of CO2 remaining is responsible for the extended shelf
life of coffee beans until grinding (Bottazzi et al., 2012). At the end of roasting,
the beans must be cooled immediately (normally using air as the cooling agent) to
prevent reactions from continuing inside the coffee bean. If this procedure fails, the
internal roast color will be darker than the external (Rovner, 2007; Burmester and
Eggers, 2010).
4.6 Roasting Techniques and Their Control

The different types of roasters vary depending on their application: domestic, com-
mercial (generally used in cafeterias), or industrial. Several patents for new roaster
designs arrive on the market every year, but generally they operate by indirect heat-
ing (heat from burning gases—convection) or direct heating (the heat passes to the
coffee beans through roaster walls—conduction). The amount of energy necessary
to heat resistances is much higher than in infrared or microwave sources. Roasters
can also be classified as continuous, where the grains are fed and withdrawn continu-
ously, and as a batch, where the beans are withdrawn after the roasting cycle is com-
pleted (Clarke and Vitzthum, 2001). Table 4.4 shows a technical comparison among
the main roaster types, and Figure 4.3b presents two models of industrial and com-
mercial roasters. Basic roasting control was established by SCAA, Specialty Coffee
Association of America, through numbered disks with usual color variation of roasted
coffee (Figure 4.3c). These numbers were established from temperature ranges used
for roasting. Thus, for example, Agtron 65 is related to 215–220°C (Bressani, 2011).
Another roasting control is to measure the bean weight during the roasting process.
Methods based on the bean color measured by colorimeters (visible) and infrared
devices are also used (Agtron, 1997).
4.7 Roast Standards X Regional Roast Preferences

Roast preferences vary a lot between and even inside countries. In Brazil, for exam-
ple, preferences vary from Agtron 45 (moderately dark) to Agtron 65 (light medium).
Denmark and Norway prefer some cocoa color without superficial oil. In the United
States, the most commonly used roast is 205–215°C (Agtron 50–60—medium). The
French roast is a style of coffee characterized by beans that have been roasted to
almost the burning point. This is the darkest, but still a palatable roast. Beyond the
TABLE 4.4
Types of Roasters
Type Characteristics
Rotating drum Direct heating by hot drum walls and indirect heating by convective
flow of hot gases
Can be solid or perforated—the perforations are small enough to
retain coffee beans but large enough to pass chaff, resulting in less
burnt notes. Batch or continuously operated
Gas temperatures: 400–550°C
Fixed drum Direct heating and convective flow of hot gases
Usually paddle mixers
Batch operated

Bowl Direct heating and convective flow of hot gases
Centrifugal force throws the beans up the sides of the spinning
bowl
Rotating gas temperatures: 480–550°C
Fluidized bed (HTST—high Ventilated regular and cyclic jet usually from the bottom
temperature, short time) The beans float in a hot air bed—indirect heating by
fluidizing gas
Batch operated
Spouted bed Variation of fluidized bed technique
An axial air jet causes agitation of particles
Indirect heating by fluidizing gas
Batch operated
Fast roasting: Gas temperatures: 310–360°C
Slow roasting: Gas temperatures: 230–275°C
Swirling bed Tangential gas inlet with spiral bean motion
Indirect heat transfer for a moving bean bed
Gas temperature: 280°C
Source: Adapted from Clarke, R.J. and Vitzthum, O.G. 2001. Coffee: Recent Developments.
Blackwell Science Ltd.: Oxford; Cristo, H.P. et al. 2006. J. Food Eng. 75: 142–148;
Hernández, J.A., Heyd, B., and Trystram, G. 2008. J. Food Eng. 89: 156–163; Fabbri, A.
et al. 2011. J. Food Eng. 105: 264–269.
French roast, the organic matter starts to be reduced to carbon (Bressani, 2011; Bicho
et al., 2012; Sweet Maria’s, 2013).
4.7.1 Is the Dark Roast a Tool to Mask the Poor Quality of the Grain?
The dark roast levels can hide coffee containing defects or even adulteration. Darker
roast coffee is less acidic; the high acidity of green (immature) coffee beans may
appear as astringent and bitter. This unpleasant sensorial attribute is explained mainly
by the degradation of chlorogenic acid (CGA), which releases caffeic acid and phenol
derivatives (Farah and Donangelo, 2006; Schmidt et al., 2008). Figure 4.3d is adapted
from Mello (2004) and shows a sensory pattern in roasting. In the darker roasts, the
body attribute decreases, as does the global aroma, but the burnt flavor increases,
masking other notes.
(a) (b)
Inner heat
transport
water vapor
CO2, and volatiles
Outer heat
transport by
convection/radiation
and contact
(c)
(d)
Standard Aroma Body Acidity Burnt
25 35 Roast Color disk
grayscale card classification values
Very light Tile #95
Light Tile #85

45 55 65
Moderately light Tile #75
Light medium Tile #65
Medium Tile #55

75 85 95
Coffee sensory attributes

Moderately dark Tile #45
Dark Tile #35
Very dark Tile #25

Roasting gradient
Lighter Darker
FIGURE 4.3 Coffee roast. (a) Schematic roasting process inside the coffee bean. (b) Models of industrial and commercial roasters. (c) Agtron color disks and its scale.
(d) The basic sensory pattern in roasting. ((a) Based on Clarke, R.J. and Vitzthum, O.G., Coffee: Recent Developments, Blackwell Science Ltd., Oxford, 2001; (b) Adapted
from Mello, W.L.B. Com. Tec. Embrapa, 58, 2004; (c) Reprinted with permission from Sweet Maria’s Home Coffee Roasting; (d) Reprinted with permission from Probat
Leogap.)
55
4.8 Coffee Aroma Complexity

4.8.1 How Maillard Reactions and Caramelization
Govern Coffee Flavors?
Browning of foods can occur by enzymatic or nonenzymatic mechanisms. During a
heating process, there is no enzymatic browning because enzymes are inactivated. The
Maillard reaction occurs between the carbonyl group, which is normally a reducing
sugar, and an amine that comes from an amino acid, peptide, or protein. Caramelization
is basically an interaction of sugars and needs more drastic conditions to occur (Yu et al.,
2012). The Maillard reaction was first reported by Louis-Camille Maillard (Maillard,
1912), who described that on heating sugars and amino acids in water, a brown color was
developed. Hence, a simple but efficient example of the complexity of Maillard reaction
is the reaction of glucose with ammonia that leads to the production of more than 15
compounds (Hodge, 1953; Nursten, 2005). Thus, the Maillard reaction in a food matrix
is a complex process, due to the large number of compounds present (Jaeger et al., 2010).
The various possible reaction paths taking place also depend strongly on temper-
ature and pH. These different reaction paths have been related to the intensity of
the heat treatment during food processing, especially at temperatures ranging from
100°C to 250°C and/or during storage for long periods at room temperature. Thus,
the by-products of the Maillard reaction have been present in food since humans
began cooking their meals; however, as previously mentioned, the Maillard reaction
is extremely complex and is not yet fully understood even today (Liu and Kitts, 2011).
The Hodge scheme in Figure 4.4 is the simplest form to understand the complexity
of the Maillard reaction. The step indicator H was inserted into the original scheme
(Hodge, 1953; Namiki et al., 1973; Nursten, 2005).
The Maillard reaction is divided into three main steps. At each step, there is a main reac-
tion mechanism (Nursten, 2005). Initially, the products are colorless. Reaction A starts
with a reversible condensation between a reducing sugar and an amino group, producing
an N-glycosylamine. Reaction B is an Amadori rearrangement, leading to the Amadori
compound, N-substituted 1-amino-2-deoxy-2-ketose. Reaction H (added) is a free radical
breakdown of Maillard intermediates. Reactions C are sugar dehydrations: in acid media,
furfurals, and in basic or neutral media, reductions (like ascorbic acid) are the most com-
mon. Reaction D consists of sugar fragmentation mainly by retroaldolization. Reaction E
is a Strecker degradation: α-amino acid media are oxidized to their corresponding alde-
hyde; ammonia and CO2 are transferred to other system components. In the final step, the
products are highly colored. This final stage leads to all kinds of dehydration, fragmenta-
tion, cyclization, and polymerization reactions. The Maillard’s Strecker degradation is
very important in terms of flavor formation, as the pyrazines, pyridine, heterocyclic sulfur
compounds, and sulfur furan derivatives (from sulfur amino acids) are all responsible for
the roasted coffee notes (Lee and Shibamoto, 2002; Rivera, 2008; Liu and Kitts, 2011).
Reaction F consists of an aldol condensation: aldehydes come from reactions C, D, and
E, and they react with each other by aldol condensation. Amines (including proteins) may
act as catalysts, and additional carbonyl compounds are obtained from lipid oxidation.
Reaction G is aldehyde–amine condensation: aldehydes (including α–β-insaturates) react
rapidly with amines, even at low temperatures to give melanoidins, the final products of
the Maillard reaction (melanins are the products of enzymatic browning).
The hodge scheme of maillard reactions
+amino compound –H2O

N-substituted
Aldose glycosylamine
A
Initial step B
A: Sugar–amine condensation Amadori H
B: Amadori rearrangement rearrangement
H: Free-radical reactions
1-amino-1-deoxy-2-ketose
(inserted)
C D
C –2H2O Fission products
–3H2O (acetol, butanedione,
2-oxopropanal, etc.)
Intermediate step Schiff base of HMF
C: Sugar dehydration or furfural Reductones F
D: Sugar fragmentation
E: Amino acid degradation –amino +2H –2H
(strecker) Sugars compound
+H2O E
Strecker
Dehydroreductones
degradation
+ amino acid
HMF or F –CO2
furfural E
Final step F
F Aldehydes G
F: Aldol condensation
G: Aldehyde-amine condensation Aldols and G
G N-free polymers
(heterocyclic nitrogen G
compounds) + amino + amino G + amino + amino + amino
compound compound compound compound compound
Melanoidins brown nitrogenous polymers and copolymers

FIGURE 4.4 A modified Hodge scheme for Maillard reaction. (Nursten, H.E. 2005. The Maillard Reaction: Chemistry, Biochemistry, and Implications. Reproduced
57
by permission of The Royal Society of Chemistry.)

4.8.2 Melanoidins
At the final step of the Maillard reaction, melanoidins are formed by cyclizations,
rearrangements, dehydrations, isomerizations, and condensations of low-molecular-
weight Maillard intermediates (Nunes and Coimbra, 2001; Moreira et al., 2012).
Melanoidins produced in model systems are predominantly of molecular weights
greater than 10 kDa. Melanoidins produced in foods are mostly high molecular
weight, although their formation is dependent on the heating intensity and reaction
time. Low-molecular-weight melanoidins (1–3.5 kDa) are possibly formed in the
initial stages of the Maillard reaction and then polymerize or cross-link with other
intermediates to produce high-molecular-weight melanoidins in the final stages of the
Maillard reaction (Daglia et al., 2000; Wang et al., 2011).
Although melanoidins are chemically diverse, most of them are negatively charged.
The presence of these negative charges probably contributes to the covalent or ionic
binding of CGA and this might explain the antioxidative properties observed for
coffee melanoidins. Binding of coffee flavor compounds might also occur via the
anionic groups of melanoidins and affect the sensorial attributes of coffee. However,
the type of linkage between polysaccharides, proteins, and CGAs is not well
understood (Bekedam et al., 2006).
Figure 4.5 presents a scheme from Moreira et al. (2012) and describes the coffee
melanoidin formation, although the mechanisms responsible for their formation are
still unclear. This simplified scheme shows the possible interaction among polysac-
charides, galactomannans, and arabinogalactans (the latter being mostly covalently
linked to proteins in green coffee), proteins (amino acids), and CGAs that are abun-
dant in coffee to form the approximate structure of coffee melanoidins (Borrelli et al.,
2002; Nursten, 2005; Moreira et al., 2012).
Specific information about the antioxidant activity of melanoidins is very difficult to
achieve; this is also true for other polymers in food such as the arubigins in tea or phlo-
baphenes in cocoa. Moreover, there is practically no information about the bioavail-
ability of melanoidins, although fractions with different molecular mass could possibly
present different bioavailability (Illy, 2002; Lima et al., 2009). The loss of free CGAs
and possibly other antioxidants in the roasting process, combined with the formation
of melanoidins, changes the composition and the antioxidant activity of dark-roasted
coffee (Thomas and Forbes, 2010; Liu and Kitts, 2011; Bravo et al., 2013).
The importance of melanoidins was evidenced in 1999 when the European
Community set up COST (Cooperation in Science and Technology) Action 919:
Melanoidins in Food and Health. The study ended in 2004 and among many experi-
ments in various food matrices, the group concluded that coffee has antioxidant
activity related to melanoidins (EC, 1999).
4.8.3 Caramelization and Torrefacto Roasting

Sugar degradation reactions in the absence of amino groups (caramelization—sugar
rectangle in Hodge scheme, Figure 4.4) are of importance as they lead to products
similar to Maillard reaction. However, in the Maillard reaction, the amino group acts
as a catalyst, so it is a faster reaction and higher amounts of intermediate products are
formed (Nursten, 2005). In some countries of Europe and South America, the torre-
facto roasting process is widely used. This process consists of adding sugar to coffee
Galactomannans Galactomannans
Ac Ac Ac Ac
Debranching Proteins
Depolymerization
Polymerization (transglycosylation)
Modification of the reducing end
Ac Denaturation
Depolymerization
Maillard reaction
AcAc Phenolic condensation
Ac
Ac
Ac
Chlorogenic OH
Ac OH
OH acids OH
Melanoidin populations Oxidation

Decarboxylation
O Cyclization O
O Polymerization O
OH OH
HOOC HOOC
OH OH OH OH
Debranching Legend:
Depolymerization
Mannose
Reaction of protein moiety Ac
Loss of protein moiety Acetylated mannose
Galactose
Glucose
Arabinose
Rhamnose
Glucuronic acid
Maillard reaction adduct
Unknown covalent linkage
Thermally modified arabinose side chain
Unknown material
Arabinogalactan–proteins Polypeptide chain fragment
FIGURE 4.5 Coffee melanoidins formation. (Moreira, A.S.P., Nunes F.M.M., Domingues, R. and
Coimbra, M.A., Food Funct., 3, 903–915, 2012. Reproduced by permission of The Royal Society of
Chemistry.)
at the end of the roasting cycle. This roasting technique is used in regional prefer-
ences for dark brown colors and a strong flavor with bitterness due to caramelization.
The addition of sugar at the end of the torrefacto roasting has the goal to intensify the
development of the Maillard reactions and also increase the antioxidant capacity of
coffee (López-Galilea et al., 2006; Ludwig et al., 2013).
4.8.4 Coffee Aroma Overview

Complex biochemical mechanisms are also involved in the production of the char-
acteristic flavors and coffee aromas during roasting, besides the Maillard and cara-
melization reactions. For example, the degradation of trigonelline in model roasting
results in pyridines and pyrroles (Stadler et al., 2002), and degradation (pyrolysis)
of CGAs leads to the production of phenols and flavor-active compounds, such as
2-methoxy-4-vinylphenol, 2-methoxy-4-ethylphenol, and the guaiacols, characteris-
tic of roasted coffee (Illy, 2002; Tsukui et al., 2014).
The larger classes of coffee aroma compounds are furans (caramel), pyrazines
(sweet, burnt, caramel), and phenols (spicy/astringent). However, classes of substances
such as aldehydes and ketones (sweet, fruity, and floral), pyrroles (smoky/dark roast),
and oxazoles (green, nutty, sweet) are also present. Imidazoles, alcohols, and esters
are present in coffee as minor constituents of global flavors. However, in darker roast-
ing, furan derivatives, pyradines (smoky/ash), pyrazines, and pyrroles are present in
higher amounts (Hashim and Chaveron, 1995; Flament, 2002; Boekel, 2006; Oliveira,
2007, Arruda et al., 2012).
Among the sulfur compounds, it was observed that methanethiol (toasted bread/
roast) contributes to the fresh coffee aroma, but as all the sulfur compounds are sus-
ceptible to oxidation, the coffee freshness aroma is strictly dependent on the stability
of thiols after grinding coffee and its exposure to air. Another important contribu-
tion to the qualification of coffee aroma (concentration) is the brewing method used
(Flament, 2002; Uekane et al., 2013).
4.9 Physical Changes during Coffee Bean Roasting

Inherent physical and chemical differences of coffee occur in terms of species,
varieties, origins, edaphoclimatic conditions, harvesting, processing, and roasting.
Therefore, only general remarks can be made about the physical behavior of the
beans during a gradient roasting. Table 4.5 is adapted from Sweet Maria’s data about
changes in coffee beans at diverse roasting stages (Sweet Maria’s, 2013).
4.10 Coffee Roasting: Bioactive and Antinutritional Substances

Coffee roasting promotes important modifications in the chemical parameters of the
vegetal matrix such as the destruction/formation of bioactive substances and also the
possible formation of toxic by-products.
4.10.1 General Composition of Green Coffee

The basic composition of green coffee must be known in order to understand the
important chemical changes during the roasting process. The basic chemical com-
position of green coffee is as follows: carbohydrates, polysaccharides such as
glucomannans and arabinogalactans as soluble fiber (water-soluble polysaccharides),
cellulose, disaccharides (sucrose), and monosaccharides (glucose, fructose, galactose,
arabinose, mannose, mental, xylose, and ribose) (Chu, 2012; Lim, 2013).
The lipid fraction is composed of tocopherol isomers together with the tocotri-
enols, triglycerides, fatty acids (linoleic, linolenic, oleic, palmitic, stearic, araqui-
dic, lignoceric, and behenic), sterols (stigmasterol and sitosterol), diterpenic esters,
and ceramide, besides pentacyclic diterpenic alcohols (methylcafestol, cafestol, and
kahweol) (Parras et al., 2007). These coffee diterpenes are mainly esterified with
fatty acids (such as cafestol and kahweol derivatives). Arabica coffee presents mainly
cafestol and kahweol (Figure 4.6a and b) in the lipid fraction, whereas robusta cof-
fee presents more cafestol, and minimum levels or an absence of kahweol, and has
a special marker, 16-O-metilcafestol (Campanha et al., 2010; Tsukui et al., 2014).
TABLE 4.5
The Physical Characteristic Changes of Coffee Beans According to the Roasting Level
Roasting Approximated
General Roasting Temperature
Appearance Level (˚C) Description
Green – No roast
coffee Standard humidity about 12%
Pale 130 Endothermic process of roasting begins

Light 160 Beans lose water vapor, but no physical

yellow expansion occurs
Coffee has a hay-like smell
Tan yellow 175 Beans turn a browner color. No expansion yet

The first “toast” notes can be detected
Light brown 185 Physical expansion starts

Center cut begins to open and the bean loses
silverskin
Brown 200 The bean color becomes dark brown due to the
Maillard reaction
First crack 205 The first crack starts. The sound can be similar to
popcorn pops
At this point, internal bean temperature is around
180°C
First crack 210 As first crack continues, the coffee beans start
expanding
Caramelization begins (sucrose melting point is
about 188°C)
First crack occurs due the elevated pressure in
the bean, full of water vapor and carbon dioxide
City roast 220 First crack ends
Bean expands and starts releasing carbon dioxide
City + roast 225 The coffee beans have totally finished the first
crack step
Full city 230 The coffee is near second crack

The beans start to have a light brightness
from oil
(Continued )
TABLE 4.5 (Continued )

The Physical Characteristic Changes of Coffee Beans According to the Roasting Level
Roasting Approximated
General Roasting Temperature
Appearance Level (˚C) Description
Full 235 The second crack begins
city + roast The bean cellulose matrix begins to collapse
The internal bean temperature for second crack
normally is 230°C
The stage between the first and second crack is a
period of about 15–30 s, but chemical changes
are very important
Some snap-like sounds occur

Second crack may continue into the cooling step
if the roasting process stops. This phase is
called “coasting”
Vienna 240 Coffee notes that may have distinct origins and
quality begin to be covered by the burnt flavors
The bean surface starts to be oily
French roast 245 Cellulose structure is carbonizing. The seed

expands, losing mass and bean surface is oily
The body (mouth full sensation) decreases with
degradation of the aromatic compounds, sugars,
and oils
Italian/ 250 The coffee bean can be over 25% burnt
Spanish The bitter notes are predominant
Carbonized 260 The bean is near full carbonization
Source: Reprinted with permission from Sweet Maria’s Home Coffee Roasting.
As bioactive substances, some studies have suggested that cafestol and kahweol are
responsible for increasing serum cholesterol, whereas others have linked them to
reducing the risk of cancer (Cavina et al., 2002; Chu, 2012; Tsukui et al., 2014).
Fatty acid tryptamides are another class of substances, present in coffee wax (Figure
4.6c), which, besides caffeine, are known to cause stomach irritation (Garrett et al., 2014).
The green coffee protein content includes free amino acids, mainly asparagine,
glutamic acid, alanine, aspartic acid, and lysine (Murkovic and Derler, 2006). As
secondary metabolism representatives, coffee beans also contain trigonelline
(Figure 4.6d), an alkaloid (1-methylnicotinic acid), originating from the enzymatic
methylation of nicotinic acid and several species of xanthines (pseudo alkaloids) such
as caffeine (Figure 4.6e), theobromine, and theophylline, the later, however, at much
lower levels (Clarke and Macrae, 1985b; Spiller, 1998; Nardini et al., 2002; Chu, 2012).
CGA is the major class of phenolic compounds in coffee (approximately 5 g/100 g
in Arabica and 9 g/100 g in Robusta). In fact, CGA is a class of compounds
(Figure 4.6f through k). The most important classes of CGAs in green coffee are
(a) O OH (b) O OH (c)

HO
OH OH
N
O
Cafestol Kahweol HN
O CH2(CH2)nCH3
(d) (e)
N
N+ O– N Fatty acid 5-hydroxytryptamide
N
O N
O
Trigonelline
Caffeine
O O
(f) OH (h) OH O
(g) OH
6 5
7 6
HO 1 HO
2
5 OH 7
O 4 O OH
4
3 9 8 Cinnamic acid substituents:
HO OH 2 3
HO HO OH
Cinnamic acid C3 C4 C5
Quinic acid
H OH H = p-cumaric acid 5-caffeoylquinic acid-chlorogenic acid - 5CQA
OH OH H = Caffeic acid (k) O

OH O OH
OCH3 OH H = Ferulic acid
O HO
(i) OH
O (j) O OH
HO O OH
O OH
HO O
HO OH
OH O
HO OH
O OH
O
O
5-ferruloylquinic acid - 5CFA HO OH

4,5-dicaffeoylquinic acid
5-coumaroylquinic acid
FIGURE 4.6 Chemical structures of some green coffee components.

63
derived from cinnamic acid, for example, caffeic, ferulic, p-cumaric, caffeoylquinic,
dicaffeoylquinic, feruloylquinic, p-coumaroylquinic, and caffeoylferuloylquinic
acids. The most abundant class among the CGA classes is caffeoylquinic acid with a
5-caffeoylquinic isomer (5CQA), and consequently is known as just CGA. CGAs can
also undergo polymerization reactions resulting in the production of various oligo-
mers such as dimmers, trimmers, and tetramers (Antonio et al., 2011; Parras et al.,
2007).
Biogenic amines (BAs) such as putrescine, cadaverine, serotonin, tyramine, sper-
midine, and spermine are also present in green coffee (Casal, 2004). BA levels in
the coffee matrix depend on the species, variety, ripening stage, and storage condi-
tions (Dias et al., 2012). These characteristics enable the BAs to be used as chemical
markers to determine the extent of fermentation, ripening bean status, differences
between processing methods, and even establish a criteria for the species (Arabica
and Robusta) differentiation (Casal, 2012).
Coffee beans also contain a variety of minerals, such as potassium, magnesium,
calcium, phosphorus, sulfur, lead, chromium, zinc, copper, nickel, and iron (Jaganyi
and Madlala, 2000).
4.10.2 Chemical Modifications on Roasting: Degradation

and Formation of Bioactive Molecules
The fate of many substances present in green coffee is thermal degradation (as in
most thermal food processes). However, some of these degradation reactions in the
coffee matrix are favorable as they lead to the production of substances with higher
nutritional value, flavor, and antioxidant activity, besides other desirable sensory
attributes (Wei et al., 2012).
Glucose and fructose (from sucrose) are transformed in caramelization and Maillard
reaction products. Polysaccharides are partially degraded and incorporated into mela-
noidins. The degradation of sucrose and polysaccharides also may increase the quan-
tities of organic acids such as formic, acetic, glycolic, and lactic acids (Redgwell and
Fischer, 2006; Chu, 2012). Roasting does not modify significantly the coffee lipid
fraction, except for the diterpenes; however, 0.2%–0.9% (dry weight) of these diter-
penes can still be found after the coffee has been roasted.
Depending on the roasting levels, total tocopherols may be almost totally reduced.
Derivatives of cafestol and kahweol are unstable during roasting and lead to other deriv-
atives. Nevertheless, the remaining kahweol and cafestol derivatives cannot be used as
taxonomic markers after roasting and grinding, so this distinction between Arabica and
Robusta is no longer possible (Campanha et al., 2010). However, other methods to differ-
entiate Arabica and Robusta are based on the quantification of chemical markers, such
as caffeine, trigonelline, CGAs, fatty acids, or sugars (Garrett et al., 2012).
Caffeine is stable upon roasting, but a small part is lost by sublimation (Antonio,
2011). Trigonelline is partially decomposed during roasting. At typical roasting tem-
peratures, trigonelline decomposes along two major pathways: decarboxylation and
methyl rearrangement to give pyridines and N-demethylation to give nicotinic acid
(Deby, 1994; Stadler et al., 2002). About 50% of the trigonelline remains in a light roast;
however, in a very dark roast, these remains become traces (Stennert and Maier, 1994).
CGAs are strongly affected by roasting and are degraded as a function of
time and temperature and they also give rise to flavor products or melanoidins
TABLE 4.6
General Chemical Composition of Green and Roasted Coffee
Green Coffee Roasted Coffee
Component
in g/100 g (%) Arabica Robusta Arabica Robusta
Polysaccharides 54 50 38 42
Lipids 12–18 9–13 14–20 11–16
Total CGA 4.1–7.9 6.1–11.3 1.9–2.5 3.3–3.8
Caffeine 0.9–1.3 1.5–2.5 1.1–1.3 2.4–2.5
Trigonelline 0.6–2.0 0.6–0.7 1.2–0.2 0.7–0.3
Protein 10.0–11.0 11.0–15.0 7.5–10.0 7.5–10.0
Free amino acids 0.5 0.8–1.0 – –
Volatiles – – 0.1 0.1

Minerals (ash) 3.0–4.2 4.4–4.5 4.5 4.7
Source: Adapted from Clarke, R.J. and Vitzthum, O.G., Coffee: Recent Developments, Blackwell
Science Ltd., Oxford, 2001; Mander, L. and Liu, H., Chemistry of Coffee, Elsevier Ltd.,
Hamburg, 2010; Chu, Y., Coffee: Emerging Health Effects and Disease Prevention,
New York, John Wiley and Sons Ltd., 2012; Lim, T.K., Edible Medicinal and Non-Medicinal
Plants: Fruits, volume 5, Springer Dordrecht Heidelberg, London, 2013.
(Clarke and Vitzthum, 2001; Jaiswal et al., 2012). All the major BAs were detectable
in low amounts after roasting; however, decarboxylation of amino acids or hydrolysis
of conjugated amines may occur in darker roasts, increasing the content of free BAs
(Casal, 2004; Chu, 2012). Part of the coffee protein is degraded during roasting. Free
amino acids and peptides also participate in the Strecker and Maillard reactions, and their
levels are lower in roasted coffee (Clarke and Vitzthum, 2001; Mander and Liu, 2010).
Minerals are not affected by roasting, and are almost totally present in the final
beverage because of their water solubility (Deby, 1994). Another substantial change
in coffee chemical composition is the vanillin levels that increase strongly during
the roasting process. The main mechanism is phenol decomposition via a radical-
mediated reaction with free ferulic acid (above 200°C), yielding vanillin as well as
guaiacol and 4-vinylguaiacol (Clarke and Vitzthum, 2001; Buffo and Cardelli-Freire,
2004; Parras et al., 2007). A general chemical composition for green and roasted
Arabica and Robusta coffee is shown in Table 4.6.
4.10.3 Possible Formation of Toxic By-Products

An overview of the bioorganic toxic substances that might be present in coffee shows
substances such as pesticides and mycotoxins obtained from planting, cherry process-
ing, and/or misguided storage (Rosa et al., 2011). Endogenous substances from the
roasting process also can be present and will be the focus of this discussion. Polycyclic
aromatic hydrocarbons (PAHs), furan, acrylamide, 4(5)-methylimidazole, chloropro-
panols, and traces of nitrosamines are the main concerns. Dioxins found in coffee are
reported as coming from paper filters (Raloff, 1989; Hashimoto et al., 1992). PAHs
(Figure 4.7a) are a group of chemicals that are formed by the incomplete combustion of
organic matter and are generated whenever fossil fuels or vegetation is burned; there-
fore, they are also environmental contaminants (Camargo and Toledo, 2003).
In coffee, as a result of the heavy thermal process of roasting, partial carboniza-
tion usually occurs. The formation of phenanthrene, anthracene, and benzo[g,h,i]
(a)
Fluorene Phenanthrene
Benzo[g,h,i]perylene
(b) (c) (d)

O
O NH
HO O NH2 N
O
Furan Hydroxymethyl furfural Acrylamide 4(5)-methylimidazole
(e) N
N O NH2
N
N-nitrosopyrrolidine N-nitrosamine
(f) OH CI OH CI
CI OH HO OH CI CI CI OH
3-MCPD 2-MCPD 1,3-DCP 2,3-DCP
O O
R O R O
O R R
OH O
O HO
O
CI CI CI
3-MCPD diesters 3-MCPD monoesters
FIGURE 4.7 Chemical structures of possible toxic artifacts produced in roasting process.
anthracene has been observed in some coffee bean samples. Low levels of benzo[a]
perylenes have also been noted in dark roasting under 260°C, with simultaneous par-
tial degradation of three-cycle PAHs, suggesting that transformation of low- to high-
molecular-weight PAHs occurs as the degree of roasting is increased (Houessou et al.,
2005). The transfer of PAHs to coffee infusion is less than 35%, with a slightly lower
extractability for dark-roasted coffee compared with light-roasted coffee (Bishnoi
et al., 2005; Orecchio et al., 2009; Grover et al., 2012).
PAH toxicity is measured by the toxic equivalency factor (TEF), a method devel-
oped by the U.S. Environmental Protection Agency (EPA) to evaluate structurally
related compounds with similar mechanisms of action and, therefore, similar toxic-
ity and/or carcinogenic potential. Benzo[a]pyrene (BAP) is the most dangerous and
the most studied PAH, and it has a TEF = 1. The cancer potential of other PAHs is
compared to BAP (Rosa et al., 2011).
Furan (Figure 4.7b), which is formed during the heat treatment of food and contributes
to the sensory properties of the product, has been shown to be carcinogenic in animal
experiments (EFSA, 2011a). Even in simple model systems, a large number of furanic
compounds are formed. For example, in a heated mixture of serine, threonine, and
sucrose, about 350 furans have been identified (Crews and Castle, 2007; Tock, 2011).
Furan and furan derivatives have long been known as intrinsic components of roasted
coffee. Likewise, green coffee beans contain only traces of furan. Formation of furan
during roasting is dependent on the roasting conditions (time and temperature), and is
directly linked to targeted flavor profiles (Arisseto et al., 2011). Hydroxymethylfurfural
(HMF) is a derivative from furan with alcohol and aldehyde functional groups on it
and can be metabolized to 5-sulfoxymethylfurfural, which is highly reactive and can
form adducts with deoxyribonucleic acid (DNA) or proteins (Guo et al., 2007).
Due to the high volatility of furans, any subsequent processing step or consumer
handling has an impact on its levels. Even the grinding process reduced furan levels
in roasted coffee beans by up to 40%, depending on grind size and degassing (loss of
CO2 in the micro- and macropores of the roasted bean), reducing furan levels by up to
20% in 4 h. It is estimated that only approximately 10% of the furan, initially gener-
ated during roasting, is transferred into the cup of coffee for consumption (Guenther
et al., 2010). However, coffee was consistently identified as the major contributor to
furan exposure in the adult population and showed an average contribution of 88% to
overall adult consumption (EFSA, 2011a).
Acrylamide (Figure 4.7c) is a well-known potential carcinogenic substance. In its
formation pathway, via Maillard reaction, the target amino acid is asparagine due to
its amide group. During coffee roasting, acrylamide levels reach a peak value, but
at the end of the roasting process, its final level is only a fraction of this. Therefore,
both formation and destruction of acrylamide during roasting are temperature related
(Lantz et al., 2006). Acrylamide is stable in most of the food matrices, with the excep-
tion of ground coffee, when the levels can decline during storage over the months
(Delatour et al., 2004; Hoenicke and Gatermann, 2005).
Also, 4-methylimidazole (4-MEI; Figure 4.7d) was found in commercial roasted
coffee samples ranging from 0.307 to 1.231 mg/kg but not in green coffee samples. A
significant amount of 4-MEI is formed in the Maillard reaction model system, and its
presence has been reported in commercial cola soft-drinks (Casal et al., 2002; Cunha
et al., 2011; Moon and Shibamoto, 2011).
The methylimidazole pathway in the Maillard reaction is mostly through histidine,
due to its imidazole skeleton (Nursten, 2005; Lee et al., 2012). The U.S. National
Toxicology Program (NTP) has identified 4-MEI as a carcinogenic substance. The
NTP study suggested that 4-MEI caused cancer in mice fed up to 1250 ppm of the
compound for 2 years (Clarke and Macrae, 1985c; NTP, 2007). Another toxicological
study showed that 4-MEI can induce lung carcinoma in male and female mice (Chan
et al., 2008). 4-MEI is also neurotoxic and can induce convulsions in animals (Casal
et al., 2002). Nevertheless, the European Food Safety Authority (EFSA) scientific
opinion (EFSA, 2011b) contests some of these data.
N-nitrosamines (Figure 4.7e) are nitro compounds considered to be potent car-
cinogens and may be present in a wide variety of products such as food, beverages,
and environmental samples such as soil and water, among others (Scanlan, 1983).
However, only traces of a cyclic nitrosamine named N-nitrosopyrrolidine have been
detected in roasted coffee (Deby, 1994).
The presence of chloropropanols (Figure 4.7f) in coffee is directly linked to the
temperature-roasting levels, with the darker beans producing the highest levels
(Doležal et al., 2005). There are four chloropropanols known as contaminants in

foods: 3-chloropropane-1,2-diol (3-MCPD), 2-chloropropane 1,3-diol (2-MCPD),
1,3-dichloropropanol (1,3-DCP), and 2,3-dichloropropanol (2,3-DCP). The most
common in food is 3-MCPD followed by 1,3-DCP. Chloropropanols can also be pres-
ent in food in the form of esters (EFSA, 2011c).
These substances are considered to be potential carcinogens, and have a recom-
mended daily limit of 2 mg/kg body mass. 1,3-DCP was classified by the World
Health Organization (WHO) as carcinogenic and genotoxic. However, there are no
data about the health risks of 2-MCPD and 2,3-DCP (EC, 2006; Arisseto et al., 2013).
The origin of chloropropanols in food is still obscure, but somehow it is related to
chlorine ions present in the food matrix. There are no toxicological data available on
3-MCPD esters. Complete hydrolysis of these esters in the gastrointestinal tract might
result in significant exposures to free 3-MCPD (ILSI, 2009).
4.11 Coffee Composition Parameters and Health Claims

The possible positive effects of coffee on health basically depend on the antioxidant
properties of its chemical compounds. Soluble and espresso coffees have greater anti-
oxidant activity than red wine or green tea (Vignoli et al., 2014). Caffeine antioxi-
dant activity has been neglected and overshadowed by CGA and the Maillard reaction
products (MRPs), but it has been proposed as an antioxidant against lipid peroxidation
caused by reactive oxygen species (ROS) (Ludwig et al., 2012). There are studies on
improving a roasting method to prevent the decomposition of trigonelline. Trigonelline
is known to produce an ameliorating and preventive effect on dementia. Besides that,
trigonelline decomposition produces niacin (nicotinic acid or nicotinamide). Niacin
is a substance with important nutritional and health value, and is also known as
vitamin B3 or PP (the latter name comes from antipellagra activity) (Yuji et al., 2005).
Besides their contribution to coffee flavors, CGAs are also bioactive. As an example,
dicaffeoylquinic acids that are present in both coffee and propolis have been shown to
be potent inhibitors against different types of viruses (Antonio et al., 2011).
An important example of a coffee health claim was coffee C21. In 2011, the EFSA
Panel for Dietetic Products, Nutrition and Allergies was asked to deliver an opinion
on the scientific evidence of a health claim related to coffee C21 and its supposed
reduction of spontaneous DNA strand breaks. The claim was that C21 caused a
“reduction of the amount of DNA strand breaks and of oxidative DNA damage
in white blood cells.” Coffee C21 is a blend of roasted Arabica coffees standard-
ized by their concentrations of CGAs, trigonelline, and N-methylpyridinium. The
applicant took into account five human intervention studies, one animal study, and
two in vitro studies as relevant proof for the health claim. The panel result consid-
ered that coffee C21 was sufficiently characterized. However, the cause and effect
relationship had not been established between the consumption of coffee C21 and a
reduction of spontaneous DNA strand breaks in any described human intervention,
animal, or in vitro studies. Therefore, the health claim was rejected (EFSA, 2011d).
Like any other food, the positive and negative coffee health aspects are dose
dependent. Coffee consumption has been reported as having negative effects, such as
increased gastric secretions (stomach-friendly coffees were released to fill this gap),
decreased absorption of nonheme iron, vasoconstriction, increased plasma levels of
cholesterol and homocysteine (substance associated with cardiovascular disease),

and teratogenicity from caffeine. On the other hand, coffee has been associated with
decreased neurodegenerative diseases such as Parkinson’s and Alzheimer; with the
control of type II diabetes, obesity; and the reduction of symptoms and incidence of
asthma, kidney and vesicle stones, some types of cancer (especially colon cancer), as
well an effective protection against pellagra, caries, and depression (Dórea and Costa,
2005; Alves et al., 2009; Antonio et al., 2011; Tock, 2011).
The high antioxidant potential of coffee allows its use as a natural source of these
substances in extracts and dietary supplements. Even some defective beans (brocades,
broken, green, bark, among others) that would be unacceptable to compose the flavor
of a beverage can find use in the food industry (Ramalakshmi et al., 2008). The agro-
industry has made efforts to recover waste parts of coffee during processing. Some
beverages based on whole coffee cherry (probably overripe or slightly damaged fruit)
or with the flesh of pulped coffee have been on the market for some time. Studies
for use of the silverskin lost during roasting also have been successful. Recovery of
the silverskins is based on the low amount of fats, reducing carbohydrates, and in its
antioxidant activity (Esquivel and Jiménez, 2012).
4.12 Concluding Remarks

Coffee processing is really peculiar because it involves stages of drying and roast-
ing, where the physical and chemical changes cannot be controlled very tightly. But
most of the time, these changes are welcome because they meet the requirements of
appearance and global flavor of the final beverage. In addition to planting conditions,
origin, processing, storage, and roasting, the final quality of the coffee drink will also
be affected by the grinding and brewing method. These factors define the extrac-
tion levels of the substances responsible for the aroma and taste of coffee, and also
undesirable substances such as the ones arising from a misguided processing or even
toxic artifacts typically produced in high-roasting steps.
Roasting causes changes in physical, chemical, and biological activity of coffee,
and while free natural phenolic compounds can be lost, other antioxidant compounds
are formed, in the long process from the fruit to the resulting bean. Thus, despite the
possible production of toxic by-products in high roasting, a kind of oxidative balance
can be formed with the production of other new antioxidant compounds.
After decades of studies, the way people consume coffee has changed a lot. Coffee
is no longer seen as only a stimulant or a guilty pleasure to those who really enjoy or
need an extra-long cup in the morning, but nowadays it is also seen as a beverage that
fills various criteria, such as a functional food, and thus consumers are demanding a
greater global quality in their cup.
ACKNOWLEDGMENTS
The authors thank the following companies and institutions that kindly provided
funds for the research, illustrations, and data for this chapter:
ABIC—Brazilian Coffee Industries Association

Agtron Inc.
Bureau for Competitive Intelligence of Coffee—ICAFEBR

Grão Mestre Café—ABICs Training Center
Illy Cafè
International Coffee Organization—ICO
Probat Leogap Ltd.
Sweet Maria’s Home Coffee Roasting (for the excellent photos and data)
FAPERJ
CAPES
The authors would also like to thank Embrapa Food Technology, The National
Research Council for Scientific and Technological Development (CNPQ—N.
477265/2012-0), and The Brazilian Coffee Research and Development Consortium

(Consórcio Brasileiro de Pesquisa e Desenvolvimento do Café—CBP&D).
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4

Roasting Effects on Nutritional and

Jeane Santos da Rosa, Otniel Freitas-Silva, Ronoel Luiz

4.3 Coffee Production and Consumption

Improve Coffee Quality. http://www.ico.org/docu-

4.4 Coffee Quality from Farm to Cup

4.4.1 Wet Method

4.4.2 Semidry or Pulped Natural Method: Pulped Coffee

4.4.3 Dry or Natural Method

Wet or washed method

Wash-cherries are Separation Pulp removal Beans

Cherris selection Mechanic Driving-beans still Mechanical

Usually manual Drying-whole Turn over with

FIGURE 4.2 Scheme of coffee cherry processing methods.

4.5 Coffee Roasting

4.6 Roasting Techniques and Their Control

4.7 Roast Standards X Regional Roast Preferences

Gas temperatures: 400–450°C

Light Tile #85

Medium Tile #55

Coffee sensory attributes

Very dark Tile #25

4.8 Coffee Aroma Complexity

The hodge scheme of maillard reactions

+amino compound –H2O

Melanoidins brown nitrogenous polymers and copolymers

by permission of The Royal Society of Chemistry.)

4.8.3 Caramelization and Torrefacto Roasting

Melanoidin populations Oxidation

4.8.4 Coffee Aroma Overview

4.9 Physical Changes during Coffee Bean Roasting

4.10 Coffee Roasting: Bioactive and Antinutritional Substances

4.10.1 General Composition of Green Coffee

Pale 130 Endothermic process of roasting begins

Light 160 Beans lose water vapor, but no physical

Tan yellow 175 Beans turn a browner color. No expansion yet

Light brown 185 Physical expansion starts

Full city 230 The coffee is near second crack

TABLE 4.5 (Continued )

Some snap-like sounds occur

French roast 245 Cellulose structure is carbonizing. The seed

Carbonized 260 The bean is near full carbonization

(a) O OH (b) O OH (c)

OH OH H = Caffeic acid (k) O

5-ferruloylquinic acid - 5CFA HO OH

FIGURE 4.6 Chemical structures of some green coffee components.

4.10.2 Chemical Modifications on Roasting: Degradation

Volatiles – – 0.1 0.1

4.10.3 Possible Formation of Toxic By-Products

(b) (c) (d)

Furan Hydroxymethyl furfural Acrylamide 4(5)-methylimidazole

(Doležal et al., 2005). There are four chloropropanols known as contaminants in

result in significant exposures to free 3-MCPD (ILSI, 2009).

4.11 Coffee Composition Parameters and Health Claims

cholesterol and homocysteine (substance associated with cardiovascular disease),

4.12 Concluding Remarks

ABIC—Brazilian Coffee Industries Association

Bureau for Competitive Intelligence of Coffee—ICAFEBR

477265/2012-0), and The Brazilian Coffee Research and Development Consortium

Boekel, M.A.J.S. 2006. Formation of flavour compounds in the Maillard reaction.

Ottawa: IDRC Press.

Mander, L. and Liu, H. 2010. Chemistry of Coffee. Elsevier Ltd.: Hamburg.

net/10820/537. (accessed May 27, 2013).