J Food Sci Technol (November–December 2013) 50(6):1097–1105 DOI 10.1007/s13197-011-0446-5 ORIGINAL ARTICLE Chemical composition and physical quality characteristics of Ghanaian cocoa beans as affected by pulp pre-conditioning and fermentation Emmanuel Ohene Afoakwa & Jennifer Quao & Jemmy Takrama & Agnes Simpson Budu & Firibu Kwesi Saalia Revised: 11 April 2011 /Accepted: 28 June 2011 /Published online: 15 July 2011 # Association of Food Scientists & Technologists (India) 2011 Abstract Investigations were conducted to evaluate the reductions in shell content and no appreciable changes in effects of pod storage (as a means of pulp preconditioning) germ proportions were noted. and fermentation on the chemical composition and physical characteristics of Ghanaian cocoa beans. A 4×2 full Keywords Theobroma cacao . Pod storage . Forastero . factorial design with factors as pod storage (0, 7, 14, Fermentation . Chemical composition . Physical quality 21 days) and cocoa treatment (fermented and unfermented) were conducted. Samples were analyzed for their chemical composition (moisture, crude fat, crude protein, ash and Cocoa is one of the most important agricultural export carbohydrate content) and mineral content using standard commodities in the world and forms the backbone of the analytical methods. The physical qualities of the beans were economies of some countries in West Africa, such as Cote analyzed for their proportions of cocoa nibs, shells and d’Ivoire and Ghana. Cocoa beans are the fermented and germ. Fermentation and increasing pod storage resulted in dried seeds of Theobroma cacao, and the fundamental significant (P<0.05) decreases in ash (3.48–2.92%), protein ingredient in chocolate manufacture. It is generally known (21.63–17.62%) and fat (55.21–50.40%) content of the to have originated from Central and Southern America. beans while carbohydrate content increased from 15.47% to Currently, three broad cultivars of cocoa are commonly 24.93% with both treatments. As well, increasing pod recognized: Forastero, Criollo and Trinitario. The cultivars storage and fermentation significantly (P<0.05) increased exhibit differences in the appearance of pods, yields of the copper content of the beans from while reductions in beans, flavour characteristics and in resistance to pests and Mg and K occurred. Amongst the minerals studied, disease (Wood and Lass 1985; Asiedu 1989; Afoakwa et al. potassium was the most abundant mineral followed by 2008; Afoakwa 2010; Adeyeye et al. 2010). Cocoa is magnesium, phosphorus and calcium in the fermented largely produced in developing countries, but is mostly cocoa beans. Proportion of cocoa nibs also increased from exported to and consumed in industrialized countries. with increasing pod storage and fermentation whiles Measured by volume of exports, the two main cocoa producing countries are Cote d’Ivoire and Ghana with an E. O. Afoakwa (*) : J. Quao :A. S. Budu : F. K. Saalia average annual production of ca. 40% and 20% respective- Department of Nutrition & Food Science, University of Ghana, ly, making ca. 60% of global production. In 2008, West P. O. Box LG 134, Legon, Africa alone accounted for ~71% of global cocoa supply Accra, Ghana (ICCO 2009). e-mail: e_afoakwa@yahoo.com In Ghana, cocoa has been labelled ‘the golden pod’ E. O. Afoakwa owing to the pivotal role it plays in the nation’s economy. e-mail: eafoakwa@ug.edu.gh It is cultivated on about 1.5 million hectares of land by some 800,000 families in six out of the ten regions. It is J. Takrama Cocoa Research Institute of Ghana, cultivated almost exclusively by small-holder farmers P. O. Box 8, New Tafo, Akim Eastern Region, Ghana with average farm sizes of about 4.0 ha and mean 1098 J Food Sci Technol (November–December 2013) 50(6):1097–1105 production yields of 246.4 kg/ha (Afoakwa 2010; fermentation. The pulp is the substrate metabolised during Knudsen and Fold 2011). The major cocoa type cultivated fermentation by a sequence of bacteria and fungi (Ostovar by farmers throughout Ghana is the Forastero variety with an and Keeney 1973), and since the properties of the substrate average proportions cultivated cultivars being Amazonica determine microbial development and metabolism, changes (34.4%), the Amelonado (13.3%) and the hybrid (52.3%) in the pulp may affect the production of acids by lactic acid (Afoakwa 2010). bacteria, yeasts and acetic acid bacteria. Three basic processes Cocoa beans are mostly processed into chocolate and of pulp pre-conditioning have been evaluated for the treatment cocoa products using a wide range of intermediate products of fresh cocoa beans prior to fermentation – pod storage, such as cocoa liquor, cocoa butter, cocoa cake and raw mechanical or enzymatic depulping and bean spreading cocoa powder. Cocoa powder is essentially used in (Rohan 1963; Wood and Lass 1985; Biehl et al. 1989; flavouring biscuits, ice cream and other dairy products, Schwan and Wheals 2004). drinks and cakes and in the manufacture of coatings for Traditionally, Ghanaian farmers have unknowingly confections and frozen desserts (Afoakwa et al. 2007; adopted this technique of pod storage by their practice of Pandey and Singh 2011; Frost et al. 2011; Rossini et al. using family labour to collect the harvested pods into piles 2011). It is also used in the beverage industry, for example 3–5 days before organizing friends and neighbours to help in the preparation of chocolate milk. Cocoa butter is used in break open the pods prior to fermentation (Duncan 1984). the manufacture of chocolate confectionery, soap and This method of pod storage appears to have highly cosmetics (Ntiamoah and Afrane 2008; Schumacher et al. beneficial effect on the chemical composition and subse- 2010). Other by-products such as cocoa pulp juice is also quent development of chocolate flavour, though the precise fermented to produce industrial alcohol and alcoholic chemical and biochemical effects, conditions and processes beverages such as brandy and wine (Jayathilakan et al. still remain unknown. With increasing specialty niche 2011). Currently, the pod husks and shells are used for the products in chocolate confectionery, understanding the preparation of animal feed and fertilizer in Ghana factors contributing to variations in the chemical composi- (Ntiamoah and Afrane 2008). The unique culture of tion and physical qualities of cocoa beans during pod producing high quality dried cocoa beans in Ghana, as storage and subsequent fermentation processes would have engraved in the traditional farming practices of the peasant significant commercial implications. Thus, this work farmers, coupled with rigorous research and quality investigated effects of pod storage (as a means of pulp control programmes embarked upon consistently by pre-conditioning) and fermentation on the chemical com- successive Governments to date, has guaranteed Ghanaian position and physical quality characteristics of Ghanaian cocoa its premium status on the international market. cocoa beans. Processing of cocoa beans into various cocoa and chocolate products starts with an on-farm fermentation of the beans followed by drying, and roasting during industrial Materials and methods processing. These postharvest processes are very crucial to the quality of finished products as they initiate the Materials formation of chocolate flavour precursors and the brown colour of cocoa products (Schwan et al. 1995; Adeyeye et Ripe cocoa pods from mixed hybrids were harvested from al. 2010). The fermentation process breaks down the the experimental plots of Cocoa Research Institute of mucilaginous pulp surrounding the beans and causes Ghana (CRIG), Tafo in the Eastern Region of Ghana. The cotyledon death (Sanchez et al. 1985; Gotsch 1997; cocoa pods were selected according to their ripeness and Afoakwa et al. 2008). This triggers biochemical transfor- maturity levels. The beans were pulp preconditioned by mation inside the beans, leading to reduction in bitterness storing the harvested pods for a period of time before and astringency, development of flavour precursors such as, splitting. About 1,200 pods were stored (on the cocoa free amino acids, peptides and sugars (Thompson et al. plantation) at ambient temperature (25–28 °C) and relative 2007; Kratzer et al. 2009; Rodriguez-Campos et al. 2011). humidity of 85–100% for periods of 0, 7, 14 and 21 days Cocoa fermentation is influenced by many factors such as respectively. The respective pods were then split after these type of cocoa, disease, climatic and seasonal differences predetermined storage times and fermented using the (Afoakwa 2010), turning, batch size (Lehrian and Patterson traditional heap method. 1983), quantity of beans (Mamot and Samarakhody 1984; The fermentation was done by heaping about 50 kg of Wood and Lass 1985) and also pulp pre-conditioning the extracted cocoa beans on the fermenting platform (Meyer et al. 1989). covered with banana leaves. The heaped beans were again Pulp pre-conditioning entails changing the properties of covered with banana leaves and fermented for 6 days with the pulp prior to the development of microorganisms in consecutive openings and turnings after every 48 h. J Food Sci Technol (November–December 2013) 50(6):1097–1105 1099 Samples of the unfermented beans were picked into a sterile When the digestion was completed, the solution was cooled polythene bag under aerobic conditions and after the sixth slightly and 30 ml of distilled water added. The mixture days of fermentation, for drying and subsequent analysis. was brought to boil for about 10 min and filtered hot into a After each sampling time , the samples were immediately 100 ml volumetric flask using a Whatman No. 4 filter transported to the laboratory for drying by spreading the paper. The solution was then made to the mark with cocoa beans approximately 5 cm deep on metal trays distilled water. (40 cm×60 cm), and placed in a temperature controlled, forced air oven for about 24 h at a temperature of 45–50 °C Determination of Ca, Mg, Zn, Fe, Cu, Na and K until dried (to moisture content below 8%). The dried beans were bagged in airtight black plastic bags and stored at The concentrations of Ca, Mg, Zn, Fe, Na and K were ambient temperature (25–28 °C) in a dark room free from determined using Spectra AA 220FS Spectrophotometer strong odours until used. Prior to chemical analyses, the (Varian Co., Mulgrave, Australia) with an acetylene flame. dried samples were milled using a hammer mill (Model 2A, One (1) ml aliquots of the digest was used to determine the Christy and Norris Ltd., Chelmsford, England) and the Ca, Mg, Zn, Fe, Cu, Na and K content of the samples. resulting liquor packed in a black polyethylene bags and used. Phosphorus determination Experimental design Two (2) ml aliquot of the digest was reacted with 5.0 ml molybdic acid. The molybdic acid was prepared by A 4×2 full factorial design with experimental factors as pod dissolving 25 ml of ammonium molybdate in 300 ml storage (0, 7, 14, 21 days) and cocoa treatment (fermented distilled water; with 75 ml of concentrated sulphuric acid and unfermented) were conducted. The samples were in125 ml of water to get 0.5 L of molybdic acid. One (1) ml analyzed for their chemical composition moisture, crude each of 1% Hydroquinone and 20% Sodium sulphite was fat, crude protein, ash and carbohydrate content (AOAC added in that sequence, and the solution was made up to 2005). Mineral analyses were also determined using 100 ml and allowed to stand for 30 min in order to develop Atomic Absorption Spectrophotometer. The physical qual- colour after which the absorption was measured at 680 nm. ities of the beans were analyzed for their proportions of A standard curve of colorimetric readings versus concen- cocoa nibs, shells and germ. tration of phosphorus using portions of standard phospho- rus solutions (1 ml, 2 ml and 3 ml) subjected to reactions Methods with molybdic acid, hydroquinone and sodium sulphate solutions were drawn. All readings were corrected using a Proximate analysis blank to eliminate the effect of any colour produced by the reagents. The moisture, crude fat, crude protein and ash were determined following the procedures in AOAC (2005) Physical quality analyses methods 931.04, 963.15, 970.22 and 972.15 respectively. Carbohydrate was determined using ‘by difference’ method. Percentage nib, shell and germ All the analyses were performed in triplicate and the mean values reported. The percentage nib, shell and germ were determined according to the method described by Wood and Lass Mineral analyses (1985). One hundred (100) grams of cocoa beans sample was weighed and the nibs carefully separated from the Mineral analyses were determined using AOAC (2005) shells using a sharp knife and weighed separately. The germ methods with slight modifications. About 0.5 g of the were then carefully separated from the nibs and weighed. sample was weighed into a 250 ml beaker. Twenty five ml The percentage nib, shell and germ were calculated. The (25 ml) of concentrated nitric acid was added and the analyses were carried out eight times and the mean values beaker covered with a watch glass. The sample was reported. digested with great care on a hot plate in a fume chamber until the solution was pale yellow. The solution was cooled Statistical analyses and 1 ml perchloric acid (70% HCLO4) added. The digestion was continued until the solution was colourless The data were analysed using Statgraphics software version or nearly so (the evaluation of dense white fumes was 3.0 (STSC Inc, Rockville, MD, USA) for analysis of regarded to be indicative of the removal of nitric acid). variance (ANOVA). Least significant difference (LSD) was 1100 J Food Sci Technol (November–December 2013) 50(6):1097–1105 used to separate and compare the means and significance results indicate that protein content was significantly was accepted at 5% level (p<0.05). All treatments were influenced (p<0.05) by pod storage and fermentation time conducted in triplicates and the mean values reported. (Table 2). Further analysis using Least Significance Difference (LSD) revealed that the decreases amongst the 7 and 14 days pod storage were not significantly different. Results and discussion The protein content of the fermented cocoa beans reduced from 18.80 to 17.60% by 14 days of pod storage. The Chemical composition of pulp preconditioned fermented protein content was significantly reduced after 6 days of and unfermented dried cocoa beans fermentation from 21.63 to 18.80% for the beans that were not stored (0 day pod storage) and likewise in all the beans Proximate composition that were pulp preconditioned (7, 14 and 21 days pod storage). These trends were consistent with reported Table 1 shows the proximate composition of unfermented literature by Biehl and Passern (1982), Biehl et al. and fermented cocoa beans under different pod storage (1985) and Crouzillat et al. (1999). Contrary to this, periods. The moisture levels of the cocoa beans were Aremu et al. (1995) reported a significant increase in bean considerably lower (3.89–4.95%) than the acceptable limits protein content by the sixth day of fermentation. The (6–7%) for long term storage of cocoa (Wood and Lass observed decreases in protein content with pod storage and 1985; Dand 1997; Fowler 2009) hence the beans were quite fermentation might be due to protein breakdown during brittle in nature. These relatively lower moisture content the curing process, occurred partly due to hydrolysis to attained was to ensure that virtually all microbial and amino acids and peptides and partly by conversion to enzymatic reactions had ceased. Although the fermentation insoluble forms by the action of polyphenols as well as process reduced the water content of the beans there was losses by diffusion (Afoakwa et al. 2008; Afoakwa and still considerable amount of moisture lost during drying, Paterson 2010). thus confirming previous findings (Páramo et al. 2010). Fat content or yield is an important quality index for Fermentation introduced significant variation in the mois- cocoa processors during purchasing of fermented cocoa ture levels (Table 2). Moisture levels were significantly beans. In West African fermented and dried cocoa beans, lower (p<0.05) in all pulp preconditioned fermented cocoa the fat content ranges between 56 and 58% and most beans than in the unfermented beans (Table 1) and this may Forastero cocoas fall between 55 and 59% (Rohan 1963; be ascribed to the initial higher moisture levels of Reineccius et al. 1972; Wood and Lass 1985; Afoakwa et unfermented bean samples. al. 2008). The fat content of the beans as observed in this Crude protein content ranged from about 16 to 22% study were slightly lower than the reported values. and this was comparable to literature values of 15.2– Generally, the fat content ranged from 50.40 – 53.35% 19.8% (Aremu et al. 1995; Afoakwa et al. 2008). There and 52.27 – 55.21% respectively for the pulp pre- were general decreases in crude protein with fermentation conditioned fermented and unfermented beans. The fat for all the cocoa samples. Similarly, apparent decreases content noted in the beans from the unstored pods were were observed as pod storage increased (Table 1). The 53.35% and 55.21% for the fermented and unfermented Table 1 Effect of pod storage (pulp pre-conditioning) and fermentation on proximate composition of cocoa beans Pod storage (Days) Fermentation condition Moisture (%) Protein (%)a Fat (%) Ash (%) Carbohydrate (%)b 0 Unfermented 4.2 ±0.02 21.6 ±0.83 55.2±0.10 3.5 ±0.11 15.5 ±0.63 Fermented 4.0 ±0.02 18.8 ±0.56 53.4 ±0.63 2.8 ±0.07 21.0 ±0.08 7 Unfermented 4.4 ±0.04 20.8 ±0.05 53.3 ±1.5 2.9 ±0.05 18.6 ±0.72 Fermented 4.3 ±0.09 18.2 ±0.13 52.2 ±0.05 2.3 ±0.04 23.1 ±0.54 14 Unfermented 4.2 ±0.02 19.7 ±0.06 52.5 ±0.04 3.1 ±0.01 20.5 ±0.24 Fermented 4.5 ±0.03 17.6 ±0.60 50.5 ±0.15 2.7 ±0.18 24.7 ±0.31 21 Unfermented 4.9 ±0.01 20.4 ±0.48 52.3 ±0.07 3.3 ±0.05 19.1 ±0.09 Fermented 3.8 ±0.04 17.9 ±0.07 50.4 ±0.05 2.9 ±0.09 24.9 ±0.11 a Protein (N×6.25) b Carbohydrate was obtained using by difference method Results presented are mean values of triplicate analysis±standard deviation J Food Sci Technol (November–December 2013) 50(6):1097–1105 1101 Table 2 ANOVA summary table showing F-ratios for variations in Variables Protein Fat Carbohydrate Ash Moisture proximate composition of pulp pre-conditioned fermented and Pod storage (PS) 15.3* 166.5* 47.3* 28.4* 2.4 unfermented cocoa beans Fermentation time (FT) 16.1* 543.3* 397.7* 115.9* 16.9* Interaction (PS x FT) 3.1 15.8* 3.3 3.1 23.8* * Significant at p<0.05 beans respectively. Increasing pod storage, however, caused Pod storage influenced the carbohydrate content signifi- consistent reduction in the fat content of the cocoa beans cantly (p<0.05) (Table 2). Further analysis by LSD such that after 21 days of pod storage, the fat content had showed that samples stored for 0, 7, 14 and 21 days decreased to 50.40% and 53.35% respectively for the were significantly different from each other. An apparent fermented and unfermented samples. The observed varia- inverse relationship appears to exist between the levels of tions in the fat content of the beans prior to pod storage and fat and total carbohydrate in fermenting cocoa. Conver- fermentation might be attributed to the relatively lower sion of lipid to carbohydrate via gluconeogenesis, sizes of cocoa beans used in this study. Variations in the employing the glyoxylate cycle could not be ruled out. bean sizes could also account for the observed relatively It has been indicated that this pathway normally operates lower fat content. Wood and Lass (1985) and Dand (1997) in microorganisms and germinating oil seeds (White et reported that smaller beans size results in lower fat yield. al. 1978). Analysis of variance (ANOVA) on the data revealed that The ash content of the cocoa beans decreased signifi- the fat content of the samples decreased significantly (p< cantly (p<0.05) with fermentation and was generally 0.05) with fermentation and pod storage (Tables 1 and 2) comparable to literature values (Rohan 1963; Reineccius and this corroborate studies carried out by Aremu et al. et al. 1972; Aremu et al. 1995). ANOVA indicated that the (1995) in Nigeria where the lipid content of the cocoa beans reductions in the ash contents due to fermentation and pulp decreased from 62.9% to 55.7% by the sixth day of preconditioning were significant (p<0.05), however pod fermentation. This suggests that the reductions in fat storage of 7 days were significantly lower than the other content in cocoa beans could be avoided by reducing pod storage days (Table 2). fermentation time. Again, the consistent decreases in fat content noted with increasing pod storage might have Mineral content of pulp pre-conditioned fermented resulted from the action of lipase enzymes which break- and unfermented cocoa beans down the triglyceride in the beans into its separate groups of fatty acids, thereby increasing the free fatty acids levels The effect of pulp preconditioning on the mineral compo- leading to the production of rancid flavour in the beans sition of fermented and unfermented cocoa samples are from the prolonged stored pods. shown in Table 3. Generally, there were decreases in the Carbohydrate content was significantly (p<0.05) micronutrients with fermentation and increasing pod stor- higher in fermented samples than in unfermented samples age. The differences in mineral contents for all the different (Table 2), with beans stored for 21 days prior to days of pod storage was significant (p<0.05). Also, fermentation having the highest carbohydrate content. differences among the unfermented and their corresponding Table 3 Effect of pod storage and fermentation on mineral content of cocoa beans Pod storage Fermentation Mineral content (mg/100 g) (days) condition Fe Cu Mg Zn Na Ca P K 0 Unfermented 2.7±0.04 11.1±0.03 286.8±3.19 9.7±0.06 3.4±0.01 140.2±0.60 236.6±23.08 2313.1±6.04 Fermented 2.2±0.02 8.8±0.01 364.2±1.82 10.6±0.07 2.5±0.16 170.8±0.74 195.8±0.02 2557.9±11.01 7 Unfermented 2.5±0.02 11.5±0.13 318.6±7.27 9.3±0.06 2.5±0.04 141.1±0.60 264.4±184.62 2325.4±12.3 Fermented 1.8±0.01 13.2±0.05 262.7±3.68 8.2±0.01 3.0±0.01 143.5±0.08 210.5±23.08 2164.2±10.26 14 Unfermented 2.2±0.02 13.7±0.02 331.5±6.89 9.3±0.05 3.3±0.08 158.2±0.38 292.1±23.08 2433.7±16.23 Fermented 1.5±0.03 15.5±0.06 271.3±1.16 7.5±0.02 2.6±0.06 150.3±0.68 203.9±23.08 2095.6±6.98 21 Unfermented 1.4±0.01 15.3±0.12 349.2±2.98 9.4±0.25 2.7±0.04 142.8±0.07 381.9±46.16 2318.7±3.62 Fermented 1.2±0.02 17.3±0.07 322.3±5.59 15.6±0.52 2.0±0.06 148.5±0.41 355.7±00 2070.7±5.71 Results presented are mean values of triplicate analysis±standard deviation 1102 J Food Sci Technol (November–December 2013) 50(6):1097–1105 fermented samples were also significant (p<0.05). Iron significantly different from each other but the observed generally decreased significantly (p<0.05) as pod storage significant reductions were due to the differences in values days increased and with fermentation (Table 3 and 4). The from the 0, 7 and 21 days. iron content of unfermented cocoa samples that were not Generally, phosphorus content decreased with fermenta- stored prior to fermentation was 2.73 mg/100 g and this tion at all levels of pod storage (Table 3). Contrary to these, decreased significantly by the end of the fermentation to increasing pod storage (pulp preconditioning) caused 2.21 mg/100 g by the end of the fermentation (Table 3). consistent increases in the phosphorus content (Table 3). Similar trends were observed in the beans stored for the ANOVA on the data showed that both pod storage and other days of pod storage. fermentation had significant (p<0.05) influence on the Copper content on the other hand increased as phosphorus content (Table 4). Multiple comparison test fermentation time and pod storage days increased. By (LSD) suggested that the phosphorus content at 0 and 21 days of pod storage, the copper content of both the 21 days of pulp pre-conditioning were significantly unfermented and fermented cocoa beans samples had different from each other and as well those from 7 and increased respectively from 11.1 to 15.3 mg/100 g and 14 days. 8.8 to 17.3 mg/100 g, suggesting approximately 100% Cocoa beans had very high potassium content with increase in copper content in the fermented samples. This values of 2557.92 and 2313.12 mg/100 g respectively for remarkable trend may be explained by the breakdown of both the fermented and unfermented samples from the anti-nutritional factors such as polyphenols and tannins unstored pods (Table 3). Fermentation of the beans caused during fermentation (Svanberg and Lorri 1997). Fermen- slight reduction in the samples to 2070.74 mg/100 g after tation is known to provide optimum pH conditions for the 21 days of pod storage while the unfermented samples enzymatic degradation of polyphenols which may be showed only marginal increases in K content with increas- present in the cocoa beans in the form of complexes with ing pod storage. Analysis of variance on the data showed polyvalent cations such as copper, zinc and proteins thus that the K content was significantly (p<0.05) by both rendering them unavailable. Reduction in these anti- fermentation and increasing pulp preconditioning (Table 4). nutritional factors therefore might have increased the These high values suggest that potassium is the most amount of soluble copper in several folds (Nout and abundant mineral in Ghanaian cocoa beans and these might Motarjemi 1997). have originated from the soil on which the cocoa were The magnesium content of the cocoa samples were planted. significantly higher (p<0.05) in unfermented samples than in the fermented beans (Table 4). Pod storage, however had Physical composition of pulp preconditioned fermented only marginal influence on cocoa beans with no precise and unfermented cocoa beans trends in their observation. Cocoa beans had low sodium content (2.04 to 3.35 mg/ Proportion of cocoa nibs 100 g) and were not significantly (p>0.05) influenced by fermentation although there were apparent differences The proportion of nibs ranged from 74.1 to 83.5% in the observed amongst the samples (Tables 3 and 4). On the unfermented and fermented cocoa beans that were not contrary, increasing pod storage caused general decreases in stored prior to fermentation (Fig. 1a) and these values were the sodium contents of the samples. ANOVA on the data slightly lower than those (86–90%) reported by Rohan showed that pod storage had a significant (p<0.05) (1963), Reineccius et al. (1972) and Afoakwa et al. (2008). influence on the sodium content of the cocoa beans These differences in nib content might have resulted from (Table 4). Multiple comparison test showed that the beans the harvesting season (whether major or minor) as these stored for 0 and 14 days prior to fermentation were not have been reported to affect the size of the beans (Rohan Table 4 ANOVA summary table showing F-ratios for variation in mineral content of pulp pre-conditioned fermented and unfermented cocoa beans Variables Ca Cu Na Mg Fe Zn P K Pod storage (PS) 29.3* 4945.2* 51.1* 82.0* 1341.9* 322.8* 394.3* 1053.7* Fermentation condition FC) 34.8* 2387.3* 0.1 577.3* 1365.6* 36.1* 84.5* 6180.3* Interaction (PS x FC) 54.6* 13.8* 118.0* 20.8* 80.8* 322.8* 62.3* 118.5* * Significant at p<0.05 J Food Sci Technol (November–December 2013) 50(6):1097–1105 1103 have much influence on the proportions. The amount of nib contained in the bean is of major concern to the cocoa processor since higher nib content results in higher nib recovery and fat yield. The apparent increase in weight of nib reflects a decrease in shell content. Proportion of shells Even though the shell provides adequate protection to the nib from mould and insects infestations, the shell percentage should be as low as possible (10–14%). This is because the shell is removed during processing of the cocoa beans and has very little commercial value to the processor (Rohan 1963; Reineccius et al. 1972; Wood and Lass 1985; Dand 1997; Afoakwa et al. 2008). In the unfermented cocoa beans, shell content for all the pod storage ranged between 25.1 to 12.8%. By the end of the fermentation, the shell content had decreased significantly (p<0.05) for the different pod storage days. Figure 1b shows a sharp decrease from 25.1% to 15.8% shell content for 0 days pod storage. The considerably high shell content of all the unfermented samples could be ascribed to the adhering thick mucilaginous pulp immediately surround- ing the testa prior to fermentation. Subsequent degradation of pectin by microbial pectinases during fermentation causes the liquefaction and drainage of about 10–50% of the pulp (Ouattara et al. 2008) and this might have accounted for the Fig. 1 Changes in proportion of cocoa nibs (a), shells (b)and germs relatively lower shell content in the fermented cocoa beans. (c) in pulp pre-conditioned fermented and unfermented cocoa beans Figure 1b also depicts a decrease in shell content as pod storage increased with beans stored for 21 days prior to 1963) and the important determining factors are suspected fermentation having the lowest shell content (12.8%), and to be the amount and distribution of rainfall and tempera- this could be attributed to the reduction in pulp volume by ture during the development of the pod (Rohan 1963; Wood water evaporation occurring during pod storage (Biehl et al. and Lass 1985; Dand 1997). High temperatures and lower 1989). This phenomenon could explain the decrease in shell rainfall might have accounted for the smaller nib proportion content with increasing pod storage. Multiple range test of the cocoa beans used in the study. Generally, proportion (LSD) showed that the beans stored for the different pod of nib was slightly higher in the fermented cocoa samples storage days (0, 7, 14 and 21 days) were significantly than in the unfermented samples (Fig. 1a). different from each other. The cocoa bean shells make up Pulp preconditioning and fermentation caused significant waste material thus the lower the quantity, the more increases in weight of the cocoa nibs (Table 5). As desirable it is to the cocoa processor. illustrated in Fig. 1a, the nib recovery increased with increasing pod storage days as well as fermentation. The Proportion of germ amount of pulp on the bean during shell separation would The proportion of germ for the cocoa beans ranged from 0.73 to 0.75% for all the cocoa beans (Fig. 1c) and this is similar to Table 5 ANOVA summary table showing f ratios for variation in physical constituents of pulp pre-conditioned fermented and results reported by Reineccius et al. (1972) (0.77%). Pulp unfermented cocoa beans preconditioning and fermentation time did not have any significant effect (p>0.05) on the proportion of germ of the Variables Cotyledon Shell Germ cotyledons (Table 5). Pods stored for 21 days had their beans Pod storage (A) 295.7* 281.5* 0.7 germinating and this accounted for the slightly higher Fermentation time (B) 275.7* 263.7* 0.1 proportion of germs and this observation may be attributed to pod rotting and the penetration of oxygen during pod Interaction (A x B) 118.6* 113.5* 0.6 storage (Meyer et al. 1989) hence providing favourable * Significant at p<0.05 conditions for the germination of the beans. 1104 J Food Sci Technol (November–December 2013) 50(6):1097–1105 Conclusion Crouzillat D, Lerceteau E, Rogers J, Petiard V (1999) Evolution of cacao bean proteins during fermentation: a study by two- dimensional electrophoresis. J Sci Food Agric 79:619–625 Pod storage and fermentation influenced to varied levels the Dand R (1997) The international Cocoa trade. John Wiley & Sons, chemical composition and physical characteristics of Inc, New York USA, p 102 Ghanaian cocoa beans. Chemical analysis on the samples Duncan RJE (1984) A survey of Ghanaian cocoa farmers’ fermenta- revealed that fermentation and increasing pod storage tion and drying practices and their implications for Malaysian practices. Proceedings of International Conference on Cocoa and resulted in consistent decreases in ash (minerals), protein Coconut, 15–17 October, 1984, Kuala Lumpur, Malaysia and fat content of the beans while carbohydrate content Frost DJ, Adhikari K, Lewis DS (2011) Effect of barley flour on the increased with both treatments. As well, increasing pod physical and sensory characteristics of chocolate chip cookies. J storage and fermentation increased the copper content of Food Sci Technol. doi:10.1007/s13197-010-0179-x Fowler MS (2009) Cocoa Beans: From Tree to Factory. In: Beckett ST the beans while reductions in Mg and K occurred. Amongst (ed) Industrial chocolate manufacture and use, 4th edn. Wiley- the minerals studied, potassium was the most abundant Blackwell Science, Oxford, UK, pp 137–152 mineral followed by magnesium, phosphorus and calcium Gotsch N (1997) Cocoa biotechnology: status, constraints and future in both the fermented and unfermented cocoa beans. prospects. Biotech Adv 15:333–352 ICCO (2009) ICCO document: Annual report 2007/2008. Internation- Proportion of cocoa nibs (fermentation yield) also increased al Cocoa Organization, London U.K with increasing pod storage and fermentation whiles these Jayathilakan K, Sultana K, Radhakrishna K, Bawa AS (2011) led to reductions in shell content were noted of the dried Utilization of byproducts and waste materials from meat, poultry beans. However, no appreciable changes were noted with and fish processing industries: a review. J Food Sci Technol. doi:10.1007/s13197-011-0290-7 the proportion of germs with fermentation and increasing Knudsen MH, Fold N (2011) Land distribution and acquisition pod storage. practices in Ghana’s cocoa frontier: The impact of a state- regulated marketing system. Land Use Pol 28:378–387 Acknowledgment The authors want to thank the Cocoa Research Kratzer U, Frank R, Kalbacher H, Biehl B, Wöstemeyer J, Voigt J Institute of Ghana, Tafo, Eastern Region, Ghana for providing the (2009) Subunit structure of the vicilin-like globular storage cocoa pods used in research study. protein of cocoa seeds and the origin of cocoa- and chocolate- specific aroma precursors. Food Chem 113:903–913 Lehrian DW, Patterson GR (1983) Cocoa fermentation. In: Reed G (ed) Biotechnology, a comprehensive treatise, vol. 5. Verlag References Chemie, Basel, pp 529–575 Mamot S, Samarakhody RJ (1984) Cocoa fermentation effect of surface area, frequency of turning and depth of cocoa masses. In: Afoakwa EO (2010) Chocolate science and technology. Wiley- International Conference on Cocoa and Coconut, 15–17 October, Blackwell Publishers, Oxford, UK, pp 3–22 1984, Kuala Lumpur, Malaysia. Afoakwa EO, Paterson A (2010) Cocoa fermentation: chocolate Meyer B, Biehl B, Said M, Samarakoddy RJ (1989) Postharvest pod flavour quality. Encyclopedia of biotechnology in agriculture storage: a method for pulp preconditioning to impair strong nib and food. Taylor & Francis Publishing Inc., Oxford, U.K, pp acidification during cocoa fermentation in Malaysia. J Sci Food 457–468 Agric 48:285–304 Afoakwa EO, Paterson A, Fowler M, Ryan A (2008) Flavour Nout MJR, Motarjemi Y (1997) Assessment of fermentation as a formation and character in cocoa and chocolate: a critical review. household technology for improving food safety: a joint FAO/ Crit Rev Food Sci Nutr 48:840–857 WHO workshop. Food Cont 8:221–226 Afoakwa EO, Paterson A, Fowler M (2007) Factors influencing Ntiamoah A, Afrane G (2008) Environmental impacts of cocoa rheological and textural qualities in chocolate – a review. Trends production and processing in Ghana: life cycle assessment Food Sci Technol 18:290–298 approach. J Cleaner Prod 16:1735–1740 Adeyeye EI, Akinyeye RO, Ogunlade I, Olaofe O, Boluwade JO Ostovar K, Keeney PG (1973) Isolation and characterization of (2010) Effect of farm and industrial processing on the amino acid microorganisms involved in the fermentation of Trinidad’s cacao profile of cocoa beans. Food Chem 118:357–363 beans. J Food Sci 38:611–617 Aremu CY, Agiang MA, Ayatse JOI (1995) Nutrient and anti-nutrient Ouattara HG, Koffi BL, Karou GT, Sangare A, Niamke SL, Diopoh profiles of raw and fermented cocoa beans. Plant Foods Human JK (2008) Implication of Bacillus spp. in the production of Nutr 48:221–223 pectinolytic enzymes during cocoa fermentation. World J Micro- Asiedu JJ (1989) Processing tropical crops: a technological approach. biol Biotechnol 24:1753–1760 Macmillan Press Limited, London, pp 24–41 Pandey A, Singh G (2011) Development and storage study of reduced AOAC (2005) Official methods of analysis, 18th edn. Association of sugar soy containing compound chocolate. J Food Sci Technol Official Analytical Chemists, Washington, D.C USA 48:76–82 Biehl B, Meyer B, Crone G, Pollmann L, Said MB (1989) Páramo D, García-Alamilla P, Salgado-Cervantes MA, Robles-Olvera Chemical and physical changes in the pulp during ripening VJ, Rodríguez-Jimenes GC, García-Alvarado MA (2010) Mass and post-harvest storage of cocoa pods. J Sci Food Agric transfer of water and volatile fatty acids in cocoa beans during 48:189–208 drying. J Food Eng 99:276–283 Biehl B, Brunner E, Passern D, Quesnel VC, Adomako D (1985) Reineccius GA, Andersen DA, Kavanagh TE, Keeney PG (1972) Acidification, proteolysis and flavour potential in fermenting Identification and quantification of the free sugars in cocoa cocoa beans. J Sci Food Agric 36:583–598 beans. J Agric Food Chem 20:199–202 Biehl B, Passern D (1982) Proteolysis during fermentation-like Rodriguez-Campos J, Escalona-Buendía HB, Orozco-Avila I, Lugo- incubation of cocoa seeds. J Sci Food Agric 33:1280–1290 Cervantes E, Jaramillo-Flores ME (2011) Dynamics of volatile J Food Sci Technol (November–December 2013) 50(6):1097–1105 1105 and non-volatile compounds in cocoa (Theobroma cacao L.) Schwan RF, Wheals AE (2004) The microbiology of cocoa fermen- during fermentation and drying processes using principal tation and its role in chocolate quality. Crit Rev Food Sci Nutr components analysis. Food Res Int 44:250–258 44:205–221 Rohan TA (1963). Processing of raw cocoa for the market. FA0 Schwan RF, Rose AH, Board RG (1995) Microbial fermentation of Technical Bulletin No 60. FAO, Italy cocoa beans, with emphasis on enzymatic degradation of the Rossini K, Noreña CPZ, Brandelli A (2011) Changes in the color of pulp. J Applied Bacteriol 79:96S–107S white chocolate during storage: potential roles of lipid oxidation Svanberg U, Lorri W (1997) Fermentation and nutrient availability. and non-enzymatic browning reactions. J Food Sci Technol Food Cont 8:319–327 48:305–311 Thompson SS, Miller KB, Lopez AS (2007) Cocoa and coffee. In: Sanchez J, Daquenet G, Guiraud JP, Vincent JC, Galzy P (1985) A Doyle MP, Beuchat LR, Montville TJ (eds) Food microbiology study of the yeast flora and the effect of pure culture seedling fundamentals and frontiers. ASM Press, Washington, DC, pp during the fermentation process of cocoa beans. Lebensm - Wiss 837–850 Technol l8:69–75 White A, Handler P, Smith EL, Hill RL, Lehman IR (1978) Schumacher AB, Brandelli A, Macedo FC, Pieta L, Klug TV et al Carbohydrate metabolism I. In: White L et al (eds) Principles (2010) Chemical and sensory evaluation of dark chocolate with of biochemistry, 6th edn. McGraw Hill, New York, pp 423–476 addition of quinoa (Chenopodium quinoa Willd.). J Food Sci Wood GAR, Lass RA (1985) Cocoa, 4th edn. Longman Group, Technol 47:202–206 London, U.K