Hrana u zdravlju i bolesti, znanstveno-stručni časopis za nutricionizam i dijetetiku (2019) 8 (2) 116-122

Food in Health and Disease, scientific-professional journal of nutrition and dietetics (2019) 8 (2) 116-122

COCOA BEAN SHELL – A PROMISING BY-PRODUCT RICH

IN BIOACTIVE COMPOUNDS
Nika Pavlović1*, Maja Miškulin1, Krunoslav Aladić2, Stela Jokić3
1
Josip Juraj Strossmayer University of Osijek, Faculty of Medicine Osijek, Josipa Huttlera 4, 31000 Osijek, Croatia
2
Croatian Veterinary Institute, Branch - Veterinary Institute Vinkovci, Josipa Kozarca 24, 32100 Vinkovci, Croatia
3
Josip Juraj Strossmayer University of Osijek, Faculty of Food Technology Osijek, Franje Kuhača 20, 31000 Osijek, Croatia

review
Summary

Nowadays, when we are increasingly becoming a generation of large quantities of waste materials from various industries,
there is an emerged need for certain solutions to suppress waste or make it more economical in some other way. Some by-
products from the different food industries are rich in various bioactive compounds which could be utilized in other production
processes. Finding the purpose and use of these compounds could be valuable for future generations. One of those by-products
is cocoa bean shell (CBS), by-product in the processing of cocoa and its products, that has already proven to contain large
amount of different bioactive compounds like theobromine, caffeine, specific phenolic compounds as well as dietary fibres and
other valuable compounds which will be reviewed in this paper. CBS could be used in the production of functional products or
even in food industry, cosmetic or pharmaceutics due to its high nutritional value what also makes it an economically
acceptable raw material.

Keywords: by-product, cocoa bean shell, bioactive compounds, utilization

Introduction production of high quality dried cocoa beans. The

main process in the cocoa industry includes a wide
During the production of different products in the range of intermediate products that include cocoa
food industry, large quantities of waste are also liquor, cocoa butter, cocoa cake and raw cocoa
produced (Nguyen, 2014) that pollute the powder. Cocoa pulp juice is a by-product used in the
environment and cause major economic problems production of industrial alcohol and alcoholic
around the world. Consequently, people begin to beverages while the pod husks and shells are used as
think and explore in the direction of utilization and animal feed or fertilizer. After harvest, crucial
application of by-products from the food industry chocolate precursors are formed in the fermentation
(Manzano et al., 2017; Okiyama et al., 2017; process due to diverse biochemical transformation
Pavlović et al., 2019; Viganó et al., 2015). inside the cocoa beans. The fermentation step
The fact of growing world population and depends mostly on type of the seed, climate, season,
disappearing raw materials, with a real threat of diseases, turning, quantity of beans and pre-
reduced food sources, does not surprise that the conditioning of the pulp (Afoakwa et al., 2013). It is
awareness is raising about the needs of storage and known how during the process of fermentation
re-usage of materials that once were just a waste significant amounts of certain phenolic compounds
(Panak Balentić, 2018). Different types of waste are migrate from cocoa bean to the shell making this by-
thrown away near the factories polluting the soil, product rich in these compounds. So enriched cocoa
nearby lakes and rivers, creating the major ecological bean shell (CBS) could be a potential source of
problem while actually, those waste has the potential bioactive compounds in different industries like food,
to be reused (Hamzat and Adeola, 2011). cosmetic or pharmaceutics (Hernández-Hernández et
al., 2018). Research on waste disposal in the way of
By-products of the cocoa industry finding new solutions for the use of different by-
products would certainly reduce waste accumulation
Cocoa beans, as fermented and dried seeds of the in a world that has become serious ecological and
Theobroma cacao plant are used as a main ingredient economical problem today.
in the production of chocolate and its products. In CBS is a part of cocoa bean, which is separated from
Ghana, this raw material is called "golden pod" and the cotyledon together with the nib before or after
has a "premium status" on the market because the roasting (Arlorio et al., 2005). Since CBS is a waste
cultivation of this plant is a tradition of private farms in cocoa processing with certain bioactive
across the country, with the unique culture in the compounds (Awarikabey et al., 2014), it is necessary

*
Corresponding author: nika.felicita@gmail.com
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to further explore and find suitable applications for 2013). The higher quantities of caffeine limit the use
its usage. of CBS in animal feed depending on the species and
year of the animal (Hamzat and Adeola, 2011). The
Bioactive compounds of CBS European Union restricted the theobromine quantity
in feed to 300 mg/kg what means 13.7% w/w of CBS
While cocoa bean is only about 33% of the cocoa (Oduro-Mensah et al., 2018). Conclusions lead to the
plant, 67% is considered as waste (Campos-Vega et development of some of its removal methods so that
al., 2018). It is already known how cocoa is included such by-products can get even wider, better purpose
in the promotion of health due to the valuable and usage. Some methods of detheobromination are
bioactive compounds (Scapagnini et al., 2014) that hot water extraction, alkaline treatment as well as
can be extracted or even eliminated by various treatment by microorganisms (Adamafio, 2013).
extraction methods. In this way, its further use in the
food industry is enabled, leading again to the creation Phenolic compounds
of new technologies (Awarikabey et al., 2014).
Besides bioactive compounds (1.4%), CBS contains Phenolic compounds are secondary metabolites found
proteins (18.2%), carbohydrates (68.9%), fats (2.4%) in pigment cells of cotyledons which perform
and some minerals (9.1%) (Jurić and Nutrizio, 2014). different functions in the plant (Hernández –
CBS has been used also as fertilizer and as feed in Hernández et al., 2017). Polyphenols are involved in
animal nutrition (Afoakwa et al., 2013). plants growth and reproduction as well as in its
protection from various pests. The polyphenol profile
Methylxantines of every plant differs within the variety of each
species (Bravo, 2009). Strong antioxidant activity of
From valuable bioactive compounds, CBS primarily certain phenolic compounds reduces oxidative stress
contains methylxanthines theobromine and caffeine (Santos et al., 2017) and improves cardiovascular
while theophylline concentrations are negligible function (Aprotosoaie et al., 2016). Certain phenolic
(Okiyama et al., 2017; Pavlović et al., 2019). All compounds migrate from cocoa beans into CBS
three methylxanthines have similar psychoactive during various stages in the production process such
effects but different effects on the human organism as fermentation, roasting and alkalization, thus
(Okiyama et al., 2017). In cocoa fruit, theobromine is reducing the polyphenol content in cocoa beans and
synthesized both in pericarp and in cotyledons of increasing their content in CBS. That makes this by-
cocoa seeds. It accumulates firstly in young leaves, product rich in these compounds. Strong antioxidant
and during the ripening phase, its concentration activity of CBS could also be associated with
decrease in the pericarp while in the cotyledons its procyanidines (Ismail and Lye Yee, 2006; Okiyama
concentration increases probably due to its migration et al., 2017). The most common phenolic compounds
from the pericarp. Theobromine is synthesized from in cocoa are epicatechin (even about 35% of total
AMP (Adenosine MonoPhosphate) and metabolised phenolic content), catechin and procyanidine. Other
by demethylation via xanthine as well as in the seed cocoa bean polyphenols are galocatechin,
and leaves of the cocoa plant. The rippening phase, epigallocatehin, epicatechin-3-O-gallate, quercetin,
growing as well as soil composition and climatic quercetin 3-glucoside, quercetin-3-arabinoside,
conditions significantly affect the methylxanthine clovamide and deoxycyclovamide (Hernández-
content in cocoa plant (Smit, 2011). In the Hernández et al., 2017). During the fermentation
fermentation stage, the proportion of theobromine in process, which may last from 5 to 10 days, the
the bean is decreased by cca 25% due to the combination of endogenous and microbial enzymatic
migration of the methylxanthines from the beans to activities, with a temperature increase of about 50 °C,
the CBS (Okiyama et al., 2017; Smit, 2011; Timbie and diffusion of the metabolites inside and outside
et al., 1978). Theobromine, as naturally present in the the cotyledon, results in polymerization of
plant, serves as its defense mechanism (Hartati, polyphenols as well as their ability to react with other
2010). In addition to being toxic in larger quantities, compounds and thus the creation of certain
some authors pointed how theobromine possess many complexes. For this reason, fermentation is a very
pharmacological properties such as anticancer, important and most responsible step in reducing the
diuretic and stimulative. The use of CBS in animal content of flavan-3-ols in cocoa beans, specifically
nutrition was found questionable primarily because (-) – epicatechin. The amount of reduced polyphenols
of larger theobromine amounts which can have definitely depends on the degree of fermentation. The
adverse effects such as damage to the reproductive process of drying, after fermentation step, due to the
and developmental system of animals (Adamafio, decrease in water content also contributes to the

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reduction of polyphenols in the beans, depending Human body needs two such essential fatty acids:
mostly on climatic conditions (Di Mattia et al., 2017). linoleic (C18: 2n-6) and α-linolenic (C18: 3n-3) acid
Hernández – Hernández et al. (2017) mentions (Glick and Fischer, 2013).
different authors who refer to positive properties of In addition to interesting bioactive profile, the CBS has
phenolic compounds like antitumour, anti- also an interesting fatty acid composition, similar to that
inflammatory, antineurodegenerative, antibacterial of cocoa butter. The main fatty acids of CBS are
and anticancer properties. palmitic and oleic, while linoleic acid is even twice as
much in CBS than in cocoa butter (Okiyama et al.,
Other compounds of CBS 2017; El-Saied et al., 1981). Following the comparison
of the chemical composition of CBS fat and cocoa
Dietary fibres butter fat, it can be noticed the similarity and higher
nutritional value of CBS fat (El-Saied et al., 1981).
When consumed, dietary fibres are already known to Also, it was found how during the fermentation process
be beneficial for the human health as well as for body some microorganisms affect the changes in lipid profile
function. CBS contains about 60% dietary fibres because the content of saturated fatty acids decreases in
according to dry weight. 80% of those total fibres are CBS extracts while the content of some unsaturated
insoluble dietary fibres while 17% are soluble ones fatty acids (oleic, linoleic and gamma-linolenic fatty
and are mainly pectic substances (11.78% of the total acids) which are important for our health, increases
dietary fibres). Their amount mostly depends on (Lessa et al., 2018).
external factors such as climate and soil quality. High
day and night temperatures, with a sufficient Vitamin D
moisture, help to accumulate these compounds in
CBS. Low amount of water soluble pectins in CBS The CBS from fresh unfermented cocoa beans dried in
was reported in non-fertile and non-volcanic soils. the sun, may contain small amounts of vitamin D while
Also, the difference in the content of the water the fermented ones can contain a much larger amounts.
soluble pectins and the polyphenol content has been This is probably due to a specific precursor that is
reported previously to be in relation to the converted to vitamin D during exposure to sunlight.
heterogeneity of the seed coming from neighbor Knapp and Coward (1935) decided to make an
plantations, making the cocoa origin as a significant experiment and determine how the fermentation step, as
quality parameter (Bruna et al., 2009). well as type of drying, affect the vitamin D content in
CBS were also characterized to have the high pectin the CBS. The fermented beans are usually put on tables
ability in gel formation and is widely used in the and dried by turning in the sun during 6 days at least.
production of jams, jellies, frozen foods and foods with Some beans can be also artificially dried. Yeasts, that
reduced caloric value (Arlorio et al., 2001). The contain ergosterol, develop during the fermentation
proportion of fibre in CBS depends on whether they are process of the cocoa beans, and during the drying
roasted or not. It is also concluded that in roasted seeds process in the tropical sun, ergosterol is converted into
and shells, formation of Maillard compounds increases vitamin D. It was also noticed how this was only the
the fibre content (Redgwell et al., 2003). A positive case when CBS had been exposed to sunlight. During
constituent is that CBS contains fibres, but some the process of artificially drying, vitamin D was absent
monogastrics are unable to digest them, and because of in the CBS (Knapp and Coward, 1935). By adding a
that, some ways of improving their digestibility have CBS into animal food, it is proven the increase of
been demonstrated by fermentation with Plerotus spp., vitamin D content also in animal milk and butter
while theobromine degradation was achieved by (Knapp and Churchman, 1937).
fermentation with Aspergillus niger. Certainly, prior
using those methods, it is necessary to conduct an Biogenic amines
analysis on mycotoxicity (Bentil, 2012).
Potentially toxic compounds such as biogenic amines
Lipid profile like tyramine and the non-nutritive compounds such
as phytic acid and trypsin inhibitors, do not reduce
Fatty acids are involved in transport and storage of the possibility of further usage of CBS as a source of
energy in the body as they are essential compounds pectin. The pectin gel obtained from the CBS can be
of all membranes and are also gene regulators purified with ethanol and 2-propanol. Some studies
(Rustan and Devon, 2005). Essential fatty acids are pointed how biogenic amines can cause heart
those that are needed for the biological functioning of palpitations, hyper and hypotension, dizziness,
the body and which the body cannot synthesize itself. headache and facial redness. The amount of these

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compounds in CBS is relatively small and has no approach would be adding isolated polyphenolic
toxic effect (Arlorio et al., 2001). compounds and water-soluble pectins from CBS
further in chocolate, making it richer in antioxidant
HMF composition (Bruna et al., 2009).
Some studies have proven that the phenolic
In the food industry, because of different operation compounds of CBS that are added to some types of
conditions and due to the chemical composition of raw meat can reduce lipid oxidation with their antioxidant
materials, the synthesis of hydroxymethylfurfural properties. Therefore, they can be recommended for
(HMF), also 5-(hydroxymethyl)furfural, is a common oils that are intended for frying as a replacement for
occurrence in food. The reasons are mainly accumulation synthetic antioxidants (Okiyama et al., 2017). This
of simple sugars as well as some polysaccharides, can improve their quality and their stability without
proteins and amino acids, low pH and high temperatures affecting the color of the oil. When added to oils, the
(Kowalski et al., 2013). Jokić et al. (2018) investigated formation of free fatty acids and peroxide levels is
bioactive compounds in CBS extracts obtained after slowed down while antioxidant activity increased
subcritical water extraction (SWE) and demonstrated (Manzano et al., 2017).
how at higher temperatures HMF was detected in Looking the situation today, when economic gains and
extracts. This is one of the reasons why it is always profits are most important to the producers, the usage of
important to optimize the extraction procedure to antibiotics is increasing in livestock treatment and have
obtained desired compounds in the final extract. preventive maintenance on their health. Resistance to
Thermal treatment such as roasting (especially foods pathogenic bacteria is becoming more frequent, and
rich in carbohydrates) also greatly contributes to the excessive use of antibiotics leads to their residues in the
formation of HMF. Also, many polysaccharides are environment, which becomes serious environmental
susceptible to hydrolysis in the acidic medium and problem. Evidence is also made by various
can be transformed into simple sugars, which are confirmatory studies where traces of antibiotics are
starting material for the formation of HMF. HMF is a found in some local and waste waters. It is the reason
heterocyclic aldehyde with six carbon atoms, because some authors mention the use of by-products of
aldehyde and alcohol functional group. The basic tropical plants such as CBS as possible substitutions for
substrates of HMF formation are monosaccharides antibiotics in animal feed due to substantial
fructose and glucose, and disaccharide sucrose which antimicrobial potential, improving the health of
is easily transformed to both of them. Fructose domestic animals on farms. Bioactive compounds of
dehydration is more effective and faster than glucose those by-products can influence pathogenic bacteria,
dehydration and occurs in three stages. The last step avoiding the damage of the cell itself. Some bioactive
of dehydration forms the final structure of HMF. Due compounds may act synergistic and increase
to possible adverse effects of HMF on human health, antimicrobial activity against pathogenic bacteria.
it is necessary to take into account the reduction of Certainly, these assumptions and research require extra
this compound in food by alteration in its possible caution because some bioactive compounds may be
production (Kowalski et al., 2013). toxic (Guil-Guerrero et al., 2016).
As an adsorbent, CBS is mostly effective in removing
Some potential usage of CBS heavy metals such as lead, chrome, cadmium, etc.
There is also an increase in pH value and release of
CBS as a by-product in the cocoa industry has been calcium, magnesium, potassium and sodium from the
still discarded regardless of its high nutritional value. CBS as well (Meunier et al., 2003). Among all other
Apart from being a source of fibre, it is a potential natural materials, CBS with its low porosity is widely
source of antioxidants, due to its high phenolic used in metal decontamination of soil (Meunier et al.,
content (explained in text above), which makes it a 2004). The CBS based activated carbons show the
good source as a raw material for further use. This potential for usage as an adsorbent in various water
high content of dietary fibre makes it interesting as an or wastewater treatments, as some studies confirm
ingredient in food preparation (Martín-Cabrejas et al., (Ahmad et al., 2012). It is also recommended usage
1994; Martínez et al., 2012; Okiyama et al., 2017). of CBS in the biofiltration of wastewaters in the food
Relatively high values of dietary fibres together with production as well as biogas production. Some
phenolic compounds imply that this by-product is studies mention also the usage of phenolic extracts in
interesting to the food industry, in the manufacture of prevention of dental cavities (Okiyama et al., 2017).
confectionery products, bakery or in the preparation Other authors concluded that CBS is a promising
of low calorie dietetic and fibre-rich products (Nsor- precursor for activated carbon for usage in adsorption
Atindana et al., 2012). The another innovative of whey proteins (Pereira et al., 2014).

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The CBS can be chemically modified based on Acknowledgments

diazonium chemistry. Because of the fast, simple
preparation and the wide range of reactive functional This work has been supported by the Croatian
groups of aryl diazonium salts, they are ideal for Science Foundation under the project ―Application of
modifying surface properties of various materials and innovative techniques of the extraction of bioactive
so as the CBS. These compounds grafted on the CBS components from by-products of plant origin‖
surface changing its properties and making it a (UIP-2017-05-9909).
suitable adsorbent to remove pollutants such as heavy
metals, gases or industrial dyes (Fioresi et al., 2017). Conflicts of Interest
The CBS can be used as a fertilizer because it forms a
humus substrate, but does not decompose easily, The authors declare no conflict of interest.
which can lead to its accumulation during the season
(Nair, 2010). References
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