Changes during processing

 Fermentation

Figure 1. Phenol level of dried cocoa beans after fermentation

Figure 1 shows the total phenol content of unfermented cocoa beans is 5,00% and
decreased by 50% in 3 days of fermentation (2.33%) and 5 days to 2.13%
Phenol level decreased by approximately 50% after fermentation.
The content of polyphenol and antioxidant activity in the fermented cocoa beans is lower
than in the unfermented cocoa beans because oxidation, polymerization, and protein
binding process could reduce the polyphenol level in cocoa beans during fermentation. In
general, the fermentation process of cocoa beans may take between 5 to 7 days, and there
are two processes, namely external and internal fermentation. External fermentation is the
process of sugar catabolism by microorganisms, whereas internal fermentation includes
biochemical processes into the seed cotyledons. During the fermentation process,
polyphenol compounds disperse out of their storage cells and then undergo oxidation that
forms high molecular compounds. The decrease in phenol levels during fermentation was
suspected caused by the hydrolysis and oxidation of phenolic compounds during the
fermentation process. The decline is due to the oxidation of polyphenols by the activity of
the oxidase polyphenol enzyme (PPO). The oxidase polyphenol enzyme is an enzyme
that is essential in the process of oxidation of polyphenol compounds in cocoa. The
enzyme started working during the fermentation process and continued until the early
stages of the drying process
 Drying
Flavor development from cocoa beans precursors continues during drying with the
development of characteristic brown color. After fermentation, the beans are removed
from the heaps or boxes and dried in the sun on raised platforms covered with mats or on
the ground until fully dried within 7-8 sunny days. During the process, major polyphenol
oxidizing reactions are catalyzed by polyphenol oxidases. The content of polyphenols
decreases significantly as an effect of high temperature, diffusion of components from
beans with evaporating water, and enzymatic browning processes.
 Roasting
Roasting is the principal technological operation affecting the quality of both roasted
cocoa beans and their derived products. The cocoa beans were roasted at four different
temperatures (110–150°C) and three different air humidities (0.3–5.0%). The temperature
and duration of thermal processing strongly affected the character of physical and
chemical changes occurring in cocoa beans during roasting. Changes the antioxidant
activity of cocoa beans caused by their roasting. Although natural antioxidant compounds
are lost during heating, the overall antioxidant properties of roasted cocoa beans can be
maintained or enhanced by the formation of new antioxidants, such as the Maillard
reaction products.
The air humidity used in roasting did not affect the total phenolic content and antioxidant
activity for the lowest roasting temperature (110oC). Roasting at 110°C caused negligible
changes in total phenolic content and antioxidant activity of cocoa beans, while almost all
samples tended to have lower antioxidant potential when roasting temperature increased.
The total phenolic content in roasted cocoa beans remained unchanged or only slightly
decreased after roasting at a temperature of 110°C as compared to raw cocoa beans.
There was no effect of air humidity on phenolic content when the roasting temperature
was 110°C.
The thermal treatment conducted at higher temperatures (120 and 150°C) caused a
gradual decrease in the total phenolic level in almost all analyzed cocoa cultivars (except
cv. Forastero from Brazil). At high temperatures (120–150°C) these losses depended on
the roasting air humidity and were slightly less advanced when the air humidity was
increased from 0.3 to 5.0%. A significant rise in phenolic compounds (2.4–4.8% of the
initial content) was observed in the case of cv. Forastero from Brazil after roasting at 120
and 135°C. The increase in the phenolic content observed in this study could be
explained by the cellular structure degradation during heat treatment and in consequence
release of the bound phenolic compounds. An increase in the phenolic content after
roasting could be also explained by the polymerization or condensation of the monomeric
flavan-3-ols and anthocyanins with other phenols, and the formation of the high
molecular weight proanthocyanidins.
The roasting of the cocoa beans at 150°C led to a considerable decrease in the total
phenolic content. The application of humid air for the roasting of cocoa beans effectively
reduced the losses of phenolic compounds. This phenomenon can be explained by the
formation of the protective layer of water (present in humid air) on the surface of samples
that reduced the access of oxygen into the seeds. The greatest decrease in total phenolic
content was observed when cocoa beans were roasted at 150°C and the lowest RH
(RH=0.3%). This finding is in accordance with the fact that phenolic compounds are
easily degraded and/or become bound to polymer structures at high temperatures in the
presence of oxygen. Roasting under mentioned above conditions resulted in total
phenolics losses ranging from 2.4 to 15.2%
 Superheated steam roasting and convectional roasting
The total phenol content of cocoa beans during convection roasting and superheated
steam roasting at different temperatures (150℃, 200℃ and 250℃) for 10 − 50 min
The highest loss may occur due to high oxidation during the convectional method
because of the presence of oxygen during the roasting process. Whereas the lowest loss
may due to the absence of oxygen when roasted by the superheated steam method. Effect
of oxidative enzymes might be another factor to reduce antioxidant properties in
convection method roasting with superheated steam caused the lower loss of total
phenolics than conventional roasting of cocoa beans
The highest antioxidants were observed in roasted during superheated steam at 150℃ for
10 min and lowest at 250℃ for 50 during convectional roasting
Superheated steam roasting could be more appropriate and flexible than the convectional
method because the higher total phenol and antioxidant properties are preserved using the
same temperature and time. This method takes short time to achieve the optimum
roasting characteristics whereas the conventional method takes too long that may
contribute the loss of antioxidant properties of the products.
Figure 2. Changes in the total phenol content (TPC) of cocoa beans during convection and
superheated steam roasting at different temperatures (150oC, 200oC, and 250oC) for 10-50
min
 Vacuum roasting
During vacuum roasting of cocoa powder (45.6 and 60.8 cmHg) at temperatures 
ranging from 100 to 120°C the limited content of oxygen in the roasting space 
slowed down the oxidative degradation of catechins.
The low oxygen in the roasting space caused low oxidation of catechin which made
degradation of catechin slow. However, there was also a possibility of the degradation of
procyanidin or proanthocyanidin (precursors), as both were the constructors of catechin 
compound which made the synthesis rate always higher than the degradation rate. As the 
roasting space was vacuum, the roasting process and many of its components occurred 
faster. On the other hand, in non-vacuum roasting, high concentration of oxygen could
possibly make catechin oxidation fast.
 Vacuum roasting of 60.8 cmHg at 100° C for 25 minutes produced the highest percentage 
of catechin concentration of cocoa powder. The increased temperature to beyond 100° C f
or the length of more than 25 minutes would reduce the
catechin concentration of cocoa powder. The increased catechin in cocoa powder during 
vacuum roasting occurred due to the degradation of procyanidin (either in form of dimer, 
trimer or tetramer).
 The effect of roasting on the antioxidant properties of cocoa beans depends on the balance
between the thermal degradation of naturally occurring phenolic compounds and the formation
of new antioxidants, such as polymeric pigments and Maillard reaction products. The phenolic
content and antioxidant activity of roasted cocoa beans can be increased by thermal processing
at lower temperatures with humid air.

 Alkalization
The pH change caused by the addition of alkaline agents influenced the total polyphenols
content in the produced cocoa powder. It has turned out that natural cocoa powders (pH
5.39–5.76) showed higher levels of antioxidative capability and total content of
polyphenols. Alkalization causes high losses of polyphenols (over 60% loss of total
polyphenols content) and changes their composition. The greatest losses are observed for
epicatechin and catechin (up to ca. 98% and 80%, respectively). Further degrees of
alkalization lead to a noticeable decrease in polyphenol content. These changes may be
ascribed to the oxidation and polymerization of polyphenols under alkaline conditions.

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