Trends in Food Science & Technology 63 (2017) 103e112

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Trends in Food Science & Technology

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Review

Cocoa shell and its compounds: Applications in the food industry

Dayane C.G. Okiyama, Sandra L.B. Navarro, Christianne E.C. Rodrigues*
Separation Engineering Laboratory (LES), Department of Food Engineering (ZEA-FZEA), University of Sao Paulo (USP), P.O. Box 23, 13635-900 Pirassununga,
Sao Paulo, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Background: Cocoa shell is removed from the cocoa bean before or after the seeds are roasted; it is
Received 22 June 2016 considered a by-product of the cocoa industry that is usually underutilized or considered waste. Some
Received in revised form studies and patents have been developed in order to give a nobler destination to this material. Interest in
14 March 2017
cocoa shell is due to its high nutritional value owing to the presence of a variety of biocompounds, such
Accepted 14 March 2017
Available online 29 March 2017
as phenolic compounds, dietary fibers, theobromine and a lipid profile similar to that of cocoa butter,
besides its chocolate color and flavor.
Scope and approach: In this review, a characterization and evaluation of cocoa shell and its bio-
Keywords:
Cocoa by-products
compounds is discussed, as well as its health effects, methods for determining the main compounds, and
Cocoa waste recent applications of this by-product as a food ingredient.
Cocoa hull Key findings and conclusions: The main application of cocoa shell in the food industry is as a source of
Phenolic compounds fiber. However, studies have shown that this material has a high content of phenolic compounds,
Theobromine showing itself to have potential application as an antioxidant agent. Cocoa shell proves to be a promising
Dietary fiber ingredient in the food industry, but there have been few studies devoted to this by-product, indicating
that it is a raw material with great potential for exploration.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction 2009). Cocoa shell is considered an industrial by-product of cocoa

Cocoa (Theobroma cacao L.) is the name given to the fruit of the
cocoa tree. Its seeds are commonly called cocoa beans and consist of
an outer shell or testa surrounding two cotyledons and a small
germ (Fig. 1).
The main producing countries of cocoa beans are Co ^te d’Ivoire,
Ghana, Indonesia, Nigeria, Ecuador, Cameroon, and Brazil,
contributing almost 90% of the world's total production. World
production of cocoa beans in the 2013/2014 harvest was 4372
thousand tons, and it is estimated that for the 2014/2015 harvest,
there will be a reduction of approximately 3.2%, as can be seen in
Table 1 (International Cocoa Organization, 2016). Indeed, following
the trend of recent years, production has decreased as opposed to
consumption, which, according to Jonfia-Essien, West, Alderson,
and Tucker (2008), has increased over the last decade.
The cocoa shell is removed together with the germ before or
after roasting and the broken fragments of cotyledon, called nibs,
free of the shell, are used in chocolate production (Beckett, 2008,
* Corresponding author.
E-mail address: chrisrodrigues@usp.br (C.E.C. Rodrigues).
production that is usually underutilized or considered waste, and is
mainly used as fuel for boilers (Arlorio et al., 2005; El-Saied, Morsi,
& Amer, 1981; Fowler, 2009), although there are applications in
animal feed and fertilizer preparation (Ntiamoah & Afrane, 2008;
Prasad, Simmons, & Maher, 2004).
The presence of cocoa shell in products that are made from
cocoa beans is undesirable as it adversely affects the process and
final product quality. In this way, the shell content of cocoa prod-
ucts is an important quality parameter. In this context, the Euro-
pean Union directive on cocoa and chocolate has established the
level of shell, including germ, in cocoa nibs up to 5%, related to the
fat-free dry cocoa content (EEC, 2000). Levels higher than this value
should be regarded as a value-reduction factor. Interestingly, the
Codex Alimentarius has, for the time being, maintained that limit.
Therefore, this quality criterion of cocoa raw materials depends on
national legislation (Hug, Golay, Giuffrida, Dionisi, & Destaillats,
2006).
It is estimated that cocoa shell production is very significant,
since it represents 12%e20% of the cocoa seed (Mendes & Lima,
2007). Considering the world production of cocoa beans, the
world generation of this waste can be calculated at approximately
700 thousand tons, which is a substantial amount (International

http://dx.doi.org/10.1016/j.tifs.2017.03.007
0924-2244/© 2017 Elsevier Ltd. All rights reserved.
104 D.C.G. Okiyama et al. / Trends in Food Science & Technology 63 (2017) 103e112

2. Cocoa bean processing and its by-products and wastes

The processing of cocoa beans takes place in two stages, known

as preprocessing and processing. The first comprises the steps
carried out in the field by the cocoa producer, such as harvesting,
fruit opening, removal of the seeds with the pulp, fermentation,
drying of the beans, and storage. The process usually used in in-
dustry comprises the second phase and involves obtaining the in-
gredients used for the manufacture of chocolate and derivatives
(Beckett, 2009; Gomes, 2007). All steps involved in cocoa pre-
Fig. 1. Parts of cocoa beans. processing and processing and the generated products and
adapted from Robert (2012) byproducts, may be observed in the flowchart shown in Fig. 2.
In the processing of the product, the first step is cleaning, to
remove most of the impurities (Beckett, 2008; Dand, 1993). After
Cocoa Organization, 2016). However, when we think of the shelling
cleaning of the beans, depending on the industry in which the
waste, this amount could be even higher if we consider that along
beans are processed, they can follow two different industrial pro-
with the shell the germ and possibly part of nibs that are attached
cesses, both of which result in the same final product: cocoa mass.
to the shell are removed.
In some industries, the cocoa beans are subjected to a thermal
Recently, the value of agricultural by-products, such as the cocoa
pretreatment, followed by breaking, shelling, and winnowing and
shell, has received increasing attention due to the scarcity of nat-
only later to roasting; in other units, the whole beans are roasted
ural resources and serious environmental problems. Many re-
along with the shells, being subjected to subsequent shelling.
searchers propose the use of these by-products in applications such
The removal of the shell is an important step in the process of
as food ingredients or other value-added applications (Jahurul
obtaining the cocoa mass as some countries present legislation that
et al., 2013; Yusof, Khanahmadi, Amid, & Mahmod, 2016). Thus, a
determines the maximum value at which this residue may be
further exploration of these products as additives in foods or sup-
present in cocoa mass. In addition, to meet legal requirements,
plements of high nutritional value has gained increasing interest,
adequate removal of the shell is an important prerequisite for
primarily due to their nutritional characteristics and secondly, to
obtaining good quality product once the shell is exposed to external
the fact that their recovery can be economically attractive (Murthy
factors that allow the appearance of undesirable contaminants.
& Naidu, 2012).
These compounds do not positively contribute to the flavor and
Lately, some studies and patents have been developed, sug-
taste of the final product and may also be responsible for off-flavor.
gesting alternative applications for this material, as it is a green
Additionally, shells are fibrous materials with extremely high
material containing very interesting compounds from a nutritional
strength, a fact that can make the grind difficult and may cause
point of view, such as phenolic compounds, fibers, and a significant
abrasion to the equipment. In addition to these factors, an effective
fat content with a very interesting lipid profile, very similar to that
separation of shells and nibs influences the efficiency of the pro-
of cocoa butter (Arlorio, Coisson, Restani, & Martelli, 2001; Arlorio
cess, the loss of small nib particles along with the shell being
et al., 2005; Borchers, Keen, Hannum, & Gershwin, 2000; El-Saied
financially undesirable. Ideally, in the shelling step, the shell must
et al., 1981; Martínez et al., 2012). Conversely, this material can
be separated perfectly, releasing large parts of shells and the nibs
also present some components that need to be carefully studied, as
left practically intact (Beckett, 2009; Dand, 1993).
they are potentially toxic, such as mycotoxins and theobromine
The configuration that comprises thermal pretreatment with
(Adamafio, 2013; Brunetto et al., 2007; Copetti, Pereira, Iamanaka,
subsequent removal of the shell offers two major advantages. The
Pitt, & Taniwaki, 2010; Copetti et al., 2012).
first is that water evaporates from the beans, with a puffing effect,
Thus, the present study aims to deepen the existing knowledge
and heat increases the brittleness of the shell, making its later
about the cocoa shell and its main compounds in order to verify
removal easier. The second advantage is that thermal pretreatment
their potential use in the food industry.

Table 1
World production of cocoa beans.

Harvest 2013/2014 Estimates 2014/2015

Thousand tones Percentage (%) Thousand tones Percentage (%)

Africa 3199 73.2 3068 72.5

Cameroon 211 4.8 232 5.5
^ te d’Ivoire
Co 1746 39.9 1796 42.5
Ghana 897 20.5 740 17.5
Nigeria 248 5.7 195 4.6
Others 97 2.2 105 2.5

America 726 16.6 760 18.0

Brazil 228 5.2 230 5.4
Ecuador 234 5.4 250 5.9
Others 264 6.0 280 6.6

Asia & Oceania 447 10.2 401 9.5

Indonesia 375 8.6 325 7.7
Papua New Guinea 36 0.8 36 0.8
Others 36 0.8 40 0.9

World Total 4372 100 4230 100

adapted from International Cocoa Organization (2016)

 D.C.G. Okiyama et al. / Trends in Food Science & Technology 63 (2017) 103e112 105

Fig. 2. Cocoa bean processing and its byproducts and wastes.

leads to more homogeneous roasting because the material to be
subjected to the process is similar in size (Beckett, 2008). In fact,
there are few references in the literature about thermal pretreat-
ment, with Beckett (2008, 2009) as the main author that makes
reference to this processing step.
Beans are generally broken by a swing-hammer type of breaker.
Centrifugal force is used to break the beans against an impact plate.
The rotation of the wheel providing the centrifugal force, together
with the throughput, determine the particle size distribution for a
given quality of beans. This distribution should be as homogeneous
as possible for optimum separation of the shell from the nibs. After
breaking the shell, the nibs are separated by winnowing and un-
broken beans are returned for reprocessing. During winnowing, the
broken beans are divided into a number of fractions by means of
sieves and an air classifier, or sifter classifier, separating the shell
from the nib particle. Each section (sifter) has its own optimal air
flow, which depends upon the size fraction that is being treated
(Beckett, 2009; Gutie rrez & Perez, 2015; Minifie, 1999). In fact,
commonly, the breaking, shelling and winnowing operations occur
at the same time, in the same equipment.
Subsequently, cocoa, which may be present in different forms,
such as whole beans, nibs, or cocoa mass, must be roasted as
roasting of the nibs and cocoa mass enables a more homogeneous
process (Bertini, 1989). The conventional method for roasting of
whole beans has some critical disadvantages, among them the
great use of power, and the fact that roasting is not uniform due to
the large variability in grain size (Beckett, 2009; Fowler, 2009). In
excessively roasted whole cocoa beans, migration of part of the
106 D.C.G. Okiyama et al. / Trends in Food Science & Technology 63 (2017) 103e112
cocoa butter to the shell can be observed; as the shell is discarded,
there is loss of this compound (Minifie, 1999). On the other hand, it
can be mentioned that the advantage of subjecting whole beans to
the roasting step is that the process facilitates shell removal
(Beckett, 2009).
Following the procedures described above, one obtains the nibs,
the main product for the manufacture of chocolates and their de-
rivatives, along with the waste from this process, for instance, the
cocoa shell. This side material can be obtained dried or roasted,
depending on the industry in which cocoa beans are processed.
3. Chemical composition of cocoa shell
The composition of cocoa shell is quite variable, as is that of
cocoa beans, and will depend, among other factors, on its origin and
the processing to which it has been subjected. Some authors have
reported cocoa shell composition in their studies, as shown in
Table 2.
The protein content presented by the cocoa shell is very similar
to that of cocoa nibs (Martín-Cabrejas, Valiente, Esteban, & Molla ,
1994; Minifie, 1989). Unfortunately, it is known that 90% of the
alpha amino nitrogen in the extracted shell is strongly bound to
oxidized polyphenols found in the shell, which are converted into
polyphenoquinones. The latter compounds are combined with
protein-NH2 forming covalent bonds with the elimination of water.
It follows, therefore, that only about 1% of the protein in the cocoa
shell exists in the free condition. The possibility of extracting a
protein concentrate as a food supplement was, therefore, consid-
ered most unlikely by Greenwood-Barton (1965).
The ash content in cocoa shell seen in Table 2 is similar to the
mineral content of several seeds reported by Saura-Calixto,
Cafiellas, and Garcia-Raso (1983). The ashes of cocoa shell evalu-
ated by Osundahunsi, Bolade, and Akinbinu (2007) showed
approximately 7% sodium, 3% potassium, 33% sodium carbonate
and a pH of 10.8. In this study, the authors applied cocoa shell ash as
an alkalizing agent in the nibs and evaluated the cocoa powder and
cocoa butter produced with them. The results showed that there
were no significant differences between any of the sensory pa-
rameters for cocoa powders alkalized with ashes and the control.
Although the chocolate aroma was considered less pronounced in
the experimental samples when assessed by sensory panelists, this
did not significantly affect the overall acceptability.
Also, as can be seen in Table 2, the level of soluble sugars in
cocoa shell seems to be negligible, which represents an advantage
of this product, considering its reduced caloric value (Lecumberri
et al., 2007). The fiber content of cocoa shell is almost three times
greater than that of nibs and constitutes over 50% of the whole
material (Martín-Cabrejas et al., 1994). The fat content presents
Table 2
Chemical composition of cocoa shell (g/kg dried cocoa shell).
Martín-Cabrejas et al. (1994) Arlorio et al. (2001)
Moisture 47 ± 1 101 ± 6
Protein 116 ± 2 181 ± 8
Fat 185 ± 12 68 ± 2
Dietary fiber 504 ± 21 606 ± 6
Soluble sugars Nd Nd
Carbohydrates Nd Nd
Ash 75 ± 1 81 ± 4
Polyphenols Nd 18 ± 8
Theobromine Nd 13 ± 2
Phytic acid Nd 6±1
Others 73 Nd
Nd: not determined.
great variability, between 20 and 185 g kg
1dried cocoa shell as
shown in Table 2, and is quite a bit lower than that of nibs. In this
case, it can be suggested that an alternative to using this compound
would be to extract it using solvents, a process that is widely used
for oleaginous raw materials with low fat content (Kemper, 2005).
The amount and profile of phenolic compounds present in the
shell are very interesting as this class of compounds can show
significant antioxidant properties. These biocompounds associated
with the chemical composition profile of the cocoa shell demon-
strate that this by-product can have applicability in the food
industry.
3.1. Dietary fiber
According to the American Association of Cereal Chemists
(AACC), dietary fiber (DF) is the edible part of plants or analogous
carbohydrates that is resistant to digestion and absorption in the
human small intestine, with complete or partial fermentation in
the large intestine. DF intake has been associated in the past few
years with a great number of beneficial health effects (Howlett
et al., 2010).
Recently, research has been done in order to validate the
beneficial health effects of dietary fiber from the cocoa shell. Nsor-
Atindana, Zhong, and Mothibe (2012) prepared three dietary fiber
powders from cocoa shells by enzymatic treatment: soluble DF,
insoluble DF, and total DF. These products were evaluated for their
effects on glucose adsorption, glucose diffusion, starch hydrolysis,
cholesterol binding, sodium cholate binding, and oil binding ca-
pacities, using in vitro model systems by simulating gastric intes-
tinal conditions. They concluded that cocoa shell could be an
alternative inexpensive source of dietary fiber with additional
benefits that could be incorporated as a low calorie, bulk ingredient
in a high-fiber diet to reduce calorie and cholesterol levels and
control blood glucose levels.
The effects of soluble dietary fiber present in cocoa shell were
also studied in Zucker fatty rats by S anchez et al. (2010). Two
groups of Zucker fatty rats were fed using a standard diet (control)
and 5% of cocoa shell soluble dietary fiber, assigned as an enriched
diet. The Zucker fatty rats fed the enriched diet showed less weight
gain and food intake than those fed the standard diet. This group
also showed lower values of total cholesterol, triglycerides, and
blood pressure than the standard group. In addition, cocoa shell
soluble dietary fiber reduced plasma glucose and insulin and, as a
consequence, insulin resistance was also decreased. In this way, the
authors mentioned that cocoa shell soluble dietary fiber resulted in
an improvement of the studied risk factors associated with car-
diometabolic disorders.
Lecumberri et al. (2007), evaluating the cocoa shell, noted that
Lecumberri et al. (2007) Martínez et al. (2012)
Nd 77 ± 1
167 ± 2 150 ± 2
66 ± 4 20.2 ± 0.3
605 ± 3 Nd
3.5 ± 0.4 Nd
Nd 178.0 ± 0.9
114.2 ± 0.4 73 ± 1
58 ± 3 Nd
Nd Nd
Nd Nd
Nd Nd
 D.C.G. Okiyama et al. / Trends in Food Science & Technology 63 (2017) 103e112
of the total dietary fiber determined, 60.54% on a dry matter basis
(d.m.), only 10.09% (d.m.) consisted of soluble dietary fiber.
Exploring the hydration properties (swelling and water holding
capacity) and the glucose retardation index, they observed that the
results obtained with cocoa dietary fiber were similar to those
obtained with cellulose and carob pod fiber, these being sources of
natural, commercial insoluble dietary fiber. In this study, the au-
thors suggest that the properties of cocoa shell make it a suitable
product to be used in the preparation of low-calorie, high-fiber
foods, such as chocolate cookies, chocolate cakes, dietetic chocolate
supplements, etc., in which the color and flavor of this cocoa dietary
fiber might be advantageous.
Redgwell et al. (2003) characterized the composition of cocoa
shell dietary fiber by compositional and linkage analysis. The re-
sults showed that the polysaccharide types were diverse and
included the pectic polysaccharides (~45%), which were made up of
a heterogeneous mixture of rhamnogalacturonans with variable
degrees of branching. The hemicelluloses were also accounted for
(~20%) and consisted of a mixture of a fucosylated xyloglucan,
galactoglucomannans, and glucuronoarabinoxylan, while cellulose
accounted for ~35% of the cell wall polysaccharides. In this study,
the total DF content was approximately 40%, not as high as previ-
ously reported. This lower level was attributed to the fact that in
this study, a ‘‘Klason Lignin’’ fraction was excluded from the esti-
mation of the total dietary fiber. This fraction provided evidence
that it contained little or none lignin and, presumably, consisted
principally of protein Maillardetannin complexes. The authors
concluded that, unfortunately, the gravimetric procedures
currently in use are unable to distinguish these complexes from
legitimate lignin. In fact, their use for determining dietary fiber will
invariably lead to overestimation of dietary fiber in cocoa-derived
material.
Cocoa shell is also a source of pectin, containing approximately
9% (d.m.). Mollea, Chiampo, and Conti (2008) studied the optimi-
zation of pectin extraction from this by-product, obtaining the
highest yield, approximately 8%, when minced husks were used,
after 1 h of extraction, at pH 2.5.
To determine dietary fiber content, the AOAC standard protocols
for dietary fiber determination are commonly used (AOAC, 1984).
These protocols provide convenient, dependable procedures that
allow comparisons of dietary fiber content in different plant tissues
with accuracy and reliability. However, in order to reduce the
sources of error in the analysis, for the determination of dietary
fiber in the cocoa shell, some authors have proposed some modi-
fications of the method, as the modifications described by Man ~ as,
Bravo, and Saura-Calixto (1994) and applied for Lecumberri et al.
(2007).
3.2. Fat content
Although some authors cite the use of the cocoa shell for fat
extraction (Arlorio et al., 2005), we did not find any work relating
this process. Only El-Saied et al. (1981) performed a comparative
analysis of the cocoa shell fat and cocoa butter from the same
beans. The results showed that the physical and chemical charac-
teristics of the cocoa shell fat were almost identical to those of
cocoa butter, except with regard to acidity, as can be seen in Table 3.
The high level of acidity in cocoa shell fat can result from the hy-
drolysis of triacylglycerols. This may be due to the high tempera-
tures to which the beans are subjected during the roasting process,
as the material evaluated in this work was obtained from the
roasting of whole beans.
Regarding the fatty acid composition of cocoa shell fat and cocoa
butter, it can be observed in Table 4 that the predominant fatty
acids in cocoa butter are palmitic, stearic and oleic acids, while
107
Table 3
Some physical and chemical characteristics of cocoa butter and cocoa shell fat.
Cocoa butter Cocoa shell fat
Specific gravity at 40  C 0.9012 0.9034
Melting point ( C) 34.10 31.00
Acid value (expressed as oleic acid %) 1.68 9.12
Saponification index 191.214 205.708
Iodine index 35.57 38.73
adapted from El-Saied et al. (1981)
those in the cocoa shell fat are palmitic and oleic acids. The nutri-
tional value of cocoa shell fat is greater than that of cocoa butter, for
example, the linoleic acid content in cocoa shell fat is almost double
that of cocoa butter (El-Saied et al., 1981).
3.3. Phenolic compounds
Phenolic compounds are products of secondary metabolism of
plants, characterized as aromatic compounds having hydroxyl
groups as substituents (Haslam, 2005). Because of their antioxidant
activity, these compounds may protect cell components from
oxidative damage and consequently, can limit the risk of several
degenerative diseases associated with oxidative stress (Scalbert,
Manach, Morand, Re  mesy, & Jime
nez, 2005).
The major phenolic compounds found in cocoa are flavanols,
which include catechins, epicatechins, and procyanidins (Miller
et al., 2006; Payne et al., 2010). The high concentration of poly-
phenols prevent the consumption of fresh cocoa beans, because
these compounds give the seed a very bitter taste (Tomas-Barbera n
et al., 2007). The polyphenol content in cocoa beans may decrease
from 100% to 10% in the final product (as in chocolate); this
reduction occurs throughout different production process steps,
such as in fermentation, roasting, and alkalizing (Hannum &
Erdman, 2000). Cocoa phenolic compounds are stored in the cot-
yledons of the seeds (Andre s-Lacueva et al., 2008) and, according to
Forsyth, Quesnel, and Roberts (1958), the loss in polyphenols can
occur due to the diffusion of these compounds to the outside of the
cotyledons. Therefore, a part of the phenolic compounds present in
the cotyledons can migrate to the cocoa bean shell, generating an
enriched material in this biocompound.
From the products and by-products obtained from cocoa, cocoa
shells show a large amount of phenolic compounds and have
proved to be a good and inexpensive source of these biocompounds
with a significant antioxidant effect (Azizah, Nik Ruslawati, & Swee
Tee, 1999; Bruna, Eichholz, Rohn, Kroh, & Huyskens-Keil, 2009).
In studies of cocoa shell, Lecumberri et al. (2007) observed the
presence of polyphenolic compounds (soluble polyphenols and
tannins) associated with this material that exhibited intrinsic
antioxidant capacity. Arlorio et al. (2005) investigated the antioxi-
dant activity of phenolic and organic pigments extracted from the
cocoa shell using supercritical carbon dioxide (CO2). The results
showed that extracts rich in phenolic compounds are quite inter-
esting and can be applied as colorants and as sources of bioactive
compounds with functional properties. These sources of the com-
pound may also be responsible for antimicrobial activity, as
observed by Nsor-Atindana et al. (2012).
rez, Me
Pe ndez, Leo n, Hernandez, and Sívoli (2015), evaluating
cocoa by-products, identified procyanidins, among other com-
pounds, by qualitative analysis of the secondary metabolites found
in the cocoa shell. The proanthocyanidins found in cocoa are tan-
nins, which can vary in size starting from monomers to long-chain
polymers (Ortega et al., 2010). In vitro studies confirmed that
proanthocyanidins exhibit many biological properties related to
108 D.C.G. Okiyama et al. / Trends in Food Science & Technology 63 (2017) 103e112
Table 4
Fatty acid composition of cocoa butter and cocoa shell fat (%).
Capric (C 10:0)
Lauric (C 12:0)
Tridecanoic (C 13:0)
Myristic (C 14:0)
Myristoleic (C 14:1)
Palmitic (C 16:0)
Palmitoleic (C 16:1)
Margaric (C 17:0)
Stearic (C 18:0)
Oleic (C 18:1)
Linoleic (C 18:2)
adapted from El-Saied et al. (1981)
antioxidant activity (Counet & Collin, 2003; Miller et al., 2006).
For the determination of total content of phenolic and proan-
thocyanidin compounds in cocoa derivatives, spectrophotometric
methods are commonly used (Bruna et al., 2009; Lecumberri et al.,
2007; Payne et al., 2010). However, more recent studies using high-
performance liquid chromatography (HPLC) and even ultra per-
formance liquid chromatography (UPLC), have been reported (Ali,
Ranneh, Ismail, & Esa, 2015; Ortega et al., 2010). All methods
mentioned have shown efficiency in the identification and quan-
tification of the interest compounds.
3.4. Methylxanthines
From the various compounds present in cocoa, methylxanthines
are known for their psychoactive effects, hence the interest in their
determination in cocoa samples. Cocoa and its products are rich in
methylxanthines, caffeine (1,3,7-trimethylxanthine), theobromine
(3,7-dimethylxanthine), and theophylline. However, the latter
compound is detected in chocolate at such low levels that its
presence is usually ignored (Beckett, 2009; Conti, Paoletti, Poli, &
Visioli, 2012).
The individual compounds are thought to have similar physio-
logical effects in the body, including stimulation of the central
nervous system (CNS), cardiac muscle, and skeletal muscle, relax-
ation of smooth muscle, and diuretic effects. However, they differ
greatly in their strength of action on each body system. Cocoa
contains relatively low concentrations of caffeine, but approxi-
mately ten times as much theobromine (Beckett, 2009).
Theobromine is a white powder, and is produced mainly by the
cocoa bean shell (Fredholm, 2011). Unlike caffeine, it is a mild
stimulant of the central nervous system, and has some antioxidant
properties, as well (Azam, Hadi, Khan, & Hadi, 2003; Fredholm,
2011). The major site of theobromine synthesis is the cocoa bean
itself, whilst not excluding a minor role of theobromine migration
between the pericarp and the cocoa bean (Zheng, Koyama, Nagai, &
Ashihara, 2004). While cocoa beans are being processed, theobro-
mine content changes mainly during the fermentation stage. Dur-
ing this stage, methylxanthines migrate from the bean into the
shell, causing a decrease in cocoa bean theobromine content of
about 25% (Timbie, Sechrist, & Keeney, 1978).
Most of the studies evaluating methylxanthines and/or theo-
bromine content in cocoa analyze whole beans or their marketable
by-products (Bucheli, Rousseau, Alvarez, Laloi, & McCarthy, 2001;
Risner, 2008). Most studies that evaluated these compounds in
cocoa bean shells are in the area of animal nutrition, as this by-
product is often used in animal feed (Carvalho Junior et al., 2010;
Silva et al., 2005). Unfortunately, experiments in the area of ani-
mal nutrition have discouraged their use because these studies
Cocoa butter Cocoa shell fat
12.95 16.89
Traces Traces
Traces Traces
4.32 3.19
1.29 2.43
23.31 22.27
0.95 2.55
Traces Traces
24.51 12.05
28.74 28.16
3.93 7.49
provided evidence that high cocoa shell concentrations in the diet
are related to toxicity, notably considering theobromine as the
primary compound responsible for the toxic effects of cocoa in-
dustry by-products (Adamafio, 2013).
Nowadays, the method most used to quantify this compound is
high-performance liquid chromatography (HPLC). The advantages
of HPLC analysis of cocoa products are its efficiency, sensitivity, and
specificity in comparison with the spectrophotometric and titra-
metric methods previously described for theobromine (Naik, 2001;
Richards & Wailes, 2011).
Of the methods that employ HPLC for determination of theo-
bromine in cocoa products, the method described by Richards and
Wailes (2012) is now considered the most accepted. This method is
practical because the extraction of fat is not necessary, which
makes it less laborious. In addition, it provides higher theobromine
contents in the samples analyzed.
4. Mycotoxins in cocoa shell
Cocoa beans are susceptible to fungal contamination during
many of the processing steps. Microbial growth is affected by
intrinsic parameters of cocoa beans such as pH, water activity and
the various organic acids produced during fermentation. Besides
causing deteriorative alteration of sensorial properties, the pres-
ence of filamentous fungi in cocoa and chocolate is also a cause for
concern due to the possibility of mycotoxin formation. Both afla-
toxin and ochratoxin A have been reported in cocoa and chocolate
(Copetti, Iamanaka, Nester, Efraim, & Taniwaki, 2013; Copetti et al.,
2012).
Most contaminant fungi are present in cocoa bean shells,
especially Aspergillus, Eurotium, and Absidia species, and are
almost completely removed by winnowing (Copetti et al., 2010). It
has been reported that ochratoxin A (OTA) is concentrated in the
shell fraction, so that only a small part of the toxin contaminates the
nibs (Copetti et al., 2013; Manda et al., 2009). According to Gilmour
and Lindblom (2008), mechanical shelling removes an average of
48% (range 27%e72%) of ochratoxin A, while shelling by hand can
reduce up to 100% (Manda et al., 2009).
In another study by Copetti et al. (2012), the occurrence of af-
latoxins B1, B2, G1, and G2 in cocoa by-products was evaluated. It
was discovered that these mycotoxins were more frequent in the
cocoa shell, appearing in 11% of the samples. Therefore, it can be
inferred that the efficiency of winnowing is a critical point to
reduce the level of contaminants but, at the same time, the waste
generated at this stage results in a material rich in mycotoxins.
The mycotoxin most commonly reported in cocoa is ochratoxin
A, consequently, this mycotoxin class is the most studied in the
cocoa shell. Many studies evaluate the effectiveness of methods and
 D.C.G. Okiyama et al. / Trends in Food Science & Technology 63 (2017) 103e112
solvents for extraction/removal of ochratoxin A from the cocoa shell
(Ame zqueta, Gonza lez-Pen~ as, Lizarraga, Murillo-Arbizu, & Lo
pez de
Cerain, 2008; Arlorio et al., 2001).
Several analytical methods have been published for the deter-
mination of OTA in cocoa and cocoa products. Extraction of OTA has
been done with organic solvents on acidified samples or with
mildly alkaline aqueous bicarbonate solvents, with or without
methanol, and the extracts were either filtered or centrifuged.
Portions of the extracts were purified by passage through C18 SPE
columns or immunoaffinity columns and the purified extracts were
analyzed by ELISA, HPLC-fluorescence detector or HPLC/MS/MS
(Roberts, Chang-Yen, Bekele, Bekele, & Harrynanan, 2014). How-
ever, many authors expressed difficulties with sample extraction
(Brera, Grossi, de Santis, & Miraglia, 2003), filtration (Ame zqueta,
Gonz alez-Pen~ as, Murillo, & de Cerain, 2005; Brera et al., 2003),
long analysis times (Brera et al., 2003), and poor recoveries of OTA
from spiked samples (Ame zqueta, Gonza lez-Pen~ as, Murillo, &
 pez de Cerain, 2005).
Lo
With the aim of overcoming these problems, two methods for
OTA extraction and detection were recently proposed. Roberts et al.
(2014) developed a methodology that overcomes these problems in
cocoa and chocolate samples with a high degree of reliability.
Mishra, Gae €lle, Hayat, and Marty (2016) tested four different
extraction methods which were compared based on their re-
coveries. The best protocol was established, which involves an
organic, solvent-free extraction method for the detection of OTA in
cocoa beans using 1% sodium hydrogen carbonate (NaHCO3) in
water within 30 min. The extraction method is rapid (as compared
with existing methods), simple, reliable, and practical to perform
without complex experimental set-ups and could determine OTA at
the level 1.5 mg kg
1, which surpassed the standards set by the
European Union for cocoa (2 mg kg
1).
5. Cocoa shell applications
In addition to the conventional applications already mentioned,
and the evaluation of various compounds in the cocoa shell, recent
studies have been conducted with this material. Among them, use
as animal feed can be cited (Andrade, Pires, Carvalho, Veloso, &
Bonomo, 2010; Carvalho Junior et al., 2010; Silva et al., 2005),
with studies that were carried out in Brazil. The use of cocoa shell as
adsorbent of different compounds has been proposed (Kalaivani
et al., 2014; Ribas et al., 2014), generally applied to waste treat-
ment and used as biofiltration support for the treatment of efflu-
ents from the food industry (Turcotte, Blais, Mercier, & Drogui,
2009). Production of extracts rich in phenolic compounds with
inhibitory activity against glucosyltransferase in the prevention of
dental cavities (Kim, Park, Park, Kim, & Kwon, 2000), and biogas
production (Mancini, Papirio, Lens, & Esposito, 2016) were other
mentioned applications.
However, studies in the food area have been developed in order
to give a nobler purpose to cocoa shell; they mostly apply the cocoa
shell as an ingredient in food preparation. In this context, two
studies were conducted in order to take advantage of the high
content of dietary fiber in cocoa shell. Martínez-Cervera, Salvador,
Muguerza, Moulay, and Fiszman (2011) studied the effects of sol-
uble cocoa dietary fiber used as a fat replacer in chocolate muffins.
The authors evaluated the properties of the batter and the physical
and sensory properties of the muffins. The results indicated that
soluble cocoa dietary fiber is an option for replacing oil in a choc-
olate muffin formulation. The main advantages were that adding
soluble cocoa dietary fiber confers higher moisture and a more
tender and crumbly texture, as they were more fragile than the
control. In addition, a reduction in signs of hardening during stor-
age was observed, as well as a pleasant color. Conversely, the
109
downside was the major difficulty in chewing and swallowing the
product when a higher level of cocoa dietary fiber was added.
Additionally, a certain degree of stickiness and a bitter taste was
noted.
In another study also applying cocoa soluble dietary fiber, Collar,
Rosell, Muguerza, and Moulay (2009) investigated the effects of
increasing amounts of soluble dietary fiber from cocoa shell
(0e8%), on the preparation of fresh and stored wheat bread. It could
be observed that an increased level of cocoa-soluble dietary fibers
provided an initial softening effect. Dietary fibers from cocoa shell
added up to 6% could be used to design technologically feasible,
sensory acceptable, and long-term stored fiber-enriched wheat
bread.
In addition, the antioxidative effects of cocoa shell extracts were
tested by Amin and Yee (2006). They compared cocoa shell etha-
nolic lyophilized extract with synthetic antioxidants (BHT and b-
tocopherol) on lipid oxidation of cooked beef stored at 4  C for up to
14 days. In this study, lipid oxidation was significantly lower in
cooked beef containing cocoa shell extract compared with syn-
thetic antioxidants, and it was possible to infer that the phenolic
compounds present in the ethanolic extract of cocoa shell may
potentially reduce lipid oxidation of cooked-refrigerated beef, be-
sides presenting excellent oxidative stability.
Still in the context of the antioxidant activity of cocoa shell
extract, Aladedunye (2014) suggests its application in oils used for
frying to substitute synthetic antioxidants, such as butylated
hydroxytoluene (BHT), butylatedhydroxyanisole (BHA), and tert-
butylhydroquinone (TBHQ), which are often added to processed
oils to retard oxidative degradation during storage and frying.
At the same time, companies are taking advantage of this by-
product, and because of this, some patents using the cocoa shell
have been recorded in recent years.
In 2006, Kraft Foods patented a theobromine and phenolic
compound extraction process from the cocoa shell. In this process,
the defatted shell is initially subjected to an aqueous acetone so-
lution extraction. Next, the acetone is eliminated, thereby obtaining
an aqueous extract. Subsequently, the material goes to a filtration
gel column to separate theobromine from phenolic compounds.
Then, the column is washed to obtain an enriched theobromine
fraction. According to the inventors, cocoa shell can be used in this
process, fermented or not, toasted or not (Bradbury & Kopp, 2006).
Kraft Foods also filed a patent, which consists of alkalizing the
cocoa shell and using this material as a food additive. It was
observed that the application of this material in foods promotes
increased viscosity, such a feature may be interesting for applica-
tion in acidified dairy products such as yoghurt and cream cheese.
In addition, this product can accentuate the chocolate flavor, this
feature being interesting when the product on which it is applied
has cocoa powder as an ingredient (Chronopoulos, Zuurbier,
Brandstetter, & Jung, 2011).
Another patent filed by Barry Callebaut deals with the produc-
tion of cocoa shell powder free from heavy metals (Bernaet &
Ruysscher, 2013). This process, as well as those described by
Chronopoulos et al. (2011), consists in the alkalinization with
subsequent washing to remove the metals. The shell powder free of
heavy metals can be used as an ingredient in the food industry or as
a cocoa powder replacement. In addition to these works, Barry
Callebaut also noted that this material, when used in the manu-
facture of chocolate, prevents the occurrence of fat bloom (Bernaet
& Ruysscher, 2013).
Wang (2015) patented a process for chocolate flavor production
by preparing enzymatic hydrolysate of dried cocoa shells. As a
result, he obtained a chocolate flavor with a real chocolate aroma,
fragrance and mouth feel, which can be prepared in simple and
environmentally friendly way in that it uses a renewable source and
110 D.C.G. Okiyama et al. / Trends in Food Science & Technology 63 (2017) 103e112

Table 5
Cocoa shell applications and potential uses.

Area Product Production methods Used/potential uses Reference

Food Partially purified Extraction and precipitation with sodium Production of jams, jellies, frozen foods Arlorio et al. (2001)
pectins hexametaphosphate solution and nitric acid, and low-calorie foods.
respectively. Purification with continued
washes on a magnetic stirrer using ethanol or 2-
propanol.
Food Fiber concentrates with Washing with warm water and drying. Use as intermediate food ingredients in Martínez et al. (2012)
antioxidant properties functional foods.
Food Cocoa shell ash Incineration of cocoa shell. Production of alkalized nibs in cocoa Osundahunsi et al. (2007)
processing industries.
Food Fiber-rich product Sterilization and then grinding to 75-mm pieces. Preparation of low-calorie, high-fiber Lecumberri et al. (2007)
foods in which the color and flavor of
this product might be advantageous,
such as chocolate cookies, chocolate
cakes and dietetic chocolate
supplements.
Food Soluble cocoa fiber Obtained from cocoa shell by patented Preparation of fresh and stored wheat Collar et al. (2009);
enzymatic processes (Moulay, Ibarra, & bread; fat replacer in chocolate muffins. Martínez-Cervera et al.
Vilanova, 2006; Moulay, Sniderman, Ibarra, & (2011)
Marti, 2006).
Food Ethanolic lyophilized Extraction using ethanol 80% (v/v), filtration of Additive against lipid oxidation in Amin and Yee (2006)
extract the extract, concentrating using a rotary cooked-refrigerated beef.
evaporator and lyophilization.
Food Alkalized cocoa shell Alkalization of whole shell, drying and milling. Food additive to increase viscosity in Chronopoulos et al. (2011)
acidified dairy products, such as
yoghurt and cream cheese. It can also be
used to increase chocolate flavor.
Food Powder free from heavy Alkalization with subsequent washing to Cocoa powder replacement. Bernaet and Ruysscher
metals remove metals. (2013)
Food Chocolate flavors Enzymatic hydrolysation of cocoa shells adding Use in the production of chocolate- Wang (2015)
cellulose, protease, and glycosidase. flavored foods.
Food Extract Solvent extraction. Retardation agent used to delay Aladedunye (2014)
oxidative degradation of oils during
storage and frying.
Food/Cosmetic/
Health Cocoa shell fat enriched Extraction with solvent. Inclusion in foods, dietary supplements, Romanczyk and McClelland
in phytosterols pharmaceuticals, and cosmetics. (2004)
Food/Health Enriched theobromine Extraction with aqueous acetone solution and Manufacturing of a theobromine and Bradbury and Kopp (2006)
fraction and phenolic filtration in gel column. polyphenol enriched composition.
compound extract
Food/Health Three dietary fiber Enzymatic treatment. Incorporation in low calorie bulk Nsor-Atindana et al. (2012)
powders: soluble ingredients in high-fiber diet.
dietary fiber, insoluble
dietary fiber, and total
dietary fiber
Food/Health Extract of phenolic Extraction with supercritical CO2. Functional colorant ingredients or Arlorio et al. (2005)
compounds and antioxidant complex extract.
pigments
Agriculture Fertilizer Cocoa shell without any treatment. Additive in organic fertilizer for tomato Prasad et al. (2004)
seeds.
Animal Ingredient in the Addition of cocoa shell to elephant grass and Ruminants feeding. Andrade et al. (2010);
Nutrition formulation of elephant subsequent silage. Carvalho Junior et al. (2010)
grass silage
Animal Concentrated feed for Addition of concentrate containing 15% and 30% Feeding of lactating goats. Silva et al. (2005)
Nutrition goats cocoa shell to corn silage.
Water Activated carbon Washing of shells to remove impurities, drying Adsorption of Ni (II) ion in water Kalaivani et al. (2014)
treatment and treatment with sulfuric acid. treatment.
Effluent Biomass support Cocoa shell without any treatment. Aerobic bio-filtration process. Turcotte et al. (2009)
treatment
Health Concentrated cocoa Extraction with acetone and addition of Inhibitor against glucosyltransferase in Kim et al. (2000)
shell extract styrene-based adsorption resin for the prevention of tooth decay.
fractionation.
Energy Biogas Pretreatment with N-methylmorpholine-N- Biogas production. Mancini et al. (2016)
oxide (NMMO) and biomethane production
under controlled mesophilic conditions.

enzyme technology for its procurement. pharmaceuticals, and cosmetics.

The presence of phytosterols in the cocoa shell was also
described in a patent published by Romanczyk and McClelland
(2004). In this study, it was obtained the cocoa shell fat enriched
in phytosterols using solvent extraction. In the conclusion of the
study, the authors inferred that this material can be used as an
additive and included in foods, dietary supplements,
All the applications described in this topic and throughout the
manuscript are briefly presented in Table 5. This table shows all the
potential uses of cocoa shell in the food industry and, more
generally, in other areas, showing a wide range of applications of
this by-product.
 D.C.G. Okiyama et al. / Trends in Food Science & Technology 63 (2017) 103e112
6. Conclusions
As shown in this article, the cocoa shell presents a series of
compounds that add functional properties to the material, among
which may be mentioned phenolic compounds, theobromine, and a
high amount of dietary fiber. In addition, it presents a reasonable fat
content with a very interesting lipid profile, similar to that of cocoa
butter. This review article presents the main components of cocoa
shell, methodologies commonly applied for the determination of
these compounds, and the main applications of this by-product,
especially in the food industry.
It is concluded that cocoa shell can be applied in the food in-
dustry as a natural ingredient of great versatility. Its use as a source
of dietary fibers that act by modifying the viscosity and structure of
foods and as an ingredient for the production of extracts rich in
phenolic compounds with high antioxidant activity is highlighted.
In addition, cocoa shell also has strong brown color and chocolate
flavor, which is very interesting because it enables the application
of the product as a natural colorant and flavoring agent. Linked to
all the described applications is the fact that cocoa shell, due to its
compounds, can be considered a functional ingredient of great
value that may add flavor and bioactive characteristics to the food
to which it is added.
Besides, its application to nobler purposes has become an
important aspect of waste management, as a way to contribute to a
more environmentally friendly production in the food industry.
However, the recovery of these valuable compounds, as well as the
integral application of the cocoa shell, is an important challenge for
researchers and should be explored considering the range of po-
tential applications for cocoa shell, and the few studies carried out
with this raw material.
Acknowledgements
The authors wish to acknowledge the FAPESP (Fundaça ~o de
Amparo a Pesquisa do Estado de Sa~o Paulo - 2015/03579-5, 2014/
09446-4) and CNPq (Conselho Nacional de Desenvolvimento
gico e 303797/2016-9) for the financial support.
Científico e Tecnolo
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