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Agricultural Wastes4 (L982)225-229

COCOA SWEATINGS--AN EFFLUENT OF POTENTIAL


VALUE

M. R. ADAMS, J. DOUGAN, E. J. GLOSSOP & D. R. TWIDDY

Tropical Products Institute, 56/62 Gray's Inn Road, London WC1X 8LU, Great Britain

ABSTRACT

Cocoa sweatings are evaluated as a source of pollution. This pollution potential can
be reduced by fermentation of the sweatings to produce alcohol and/or vinegar. A t the
same time this increases the economic return to the cocoa grower. Details of the
production of alcohol and vinegarJ?om cocoa sweatings are described, together with
an analysis ~f these products.

INTRODUCTION

The cocoa beans of commerce are the product of a natural fermentation process
during which the pulp or mucilage surrounding the beans is removed. The
composition of the pulp varies according to pod maturity, cultivar, season and tree
management practice, but the pulp usually consists of approximately 80'~/,i water,
15 oj~,glucose and fructose, together with smaller quantities of citric acid, pectin,
sucrose and amino acids (Minifie, 1970). During fermentation the pulp sugars are
metabolised by a mixed flora of microorganisms to produce principally ethanol,
lactic and acetic acids. In the early stages of fermentation large quantities of liquid
known as 'sweatings' drain away from the beans. In a series of box fermentation
studies in Ghana sweatings representing 5 7 ?/o(v/w) of fresh cocoa were collected,
with 705~i of the total sweatings being produced in the first 6-10 hours of
fermentation (Dougan, 1980).
In general no attempt is made to collect or use the sweatings, although some work
has been reported in Brazil on the production of a jelly (Borges et al., 1978). West
African cocoa is a smallholder crop, the beans are fermented in heaps under
plantain leaves and the sweatings allowed to drain into the ground. In other
countries, such as Trinidad, Malaysia and Brazil, cocoa is fermented on a larger
225
Agricultural Wastes 0141-4607/82/0004-0225/$02.75 ~ Applied Science Publishers Ltd, England, 1982
Printed in Great Britain
226 M . R . ADAMS, J. DOUGAN, E. J. GLOSSOP, D. R. TWIDDY

scale in boxes at central fermentaries but again the sweatings are usually run to
waste.
The general trend to estate production of cocoa with a central fermentary and
attendant economies of scale will ultimately lead to a pollution problem caused by the
necessity of disposing of large quantities of sweatings. Occasional mention has been
made in the past of the possibility of using sweatings as a source of alcohol and
vinegar, but little detail has been given (Knapp, 1937; Adomako, 1975: Agyeman et
al., 1976). Here we report details of the composition of sweatings, their pollution
potential and the yield and composition of ethanol and vinegar made from them.

METHODS

A sample of fresh sweatings from a box fermentation in Ghana was pasteurised at


80 °C for 10 minutes, sealed in a clean bottle and air-freighted to Tropical Products
Institute, London together with a sample of sweatings which had been allowed to
ferment naturally (i.e. without the addition of yeast) at ambient temperature (30 °C).
Sweatings obtained from a box fermentation in Dominica were allowed to
ferment naturally at ambient temperature for 4 days before analysis in the country
of origin.
A sample of vinegar produced from naturally fermented sweatings which had
been further fermented aerobically to acetic acid without any inoculation was
obtained from Malaysia.

Alcohol production
The pasteurised sweatings (2 × 300 ml) in 500 ml conical flasks were inoculated
with a suspension of Saccharomyces cerevisiae (NCYC 431) obtained from a 48 h
slope (1 slope for each flask), sealed with a fermentation lock and incubated at 30 °C.
The fermentation was monitored by weight loss and was found to be complete after
7 days.

Acet~'cation
A 200 ml sample of laboratory-fermented sweatings was placed in a 1 litre conical
flask, inoculated from a slope of Acetobacter aceti subsp, orleanensis (Henneberg)
and incubated at room temperature. The fermentation, which was complete after 7
days, was monitored by periodic ethanol and acidity determinations. After filtering,
the vinegar was pasteurised at 70 °C for 20 minutes prior to bottling.

Analyses
Ethanol was determined by the dichromate oxidation procedure of Caputi &
Wright (1969).
Reducing sugars were determined by the Luff Schoorl method as described by
USES OF COCOA SWEAT1NGS 227

Browne & Zerban (1941). Total sugar was determined as reducing sugar after
inversion by refluxing for 10 minutes in 0. IN hydrochloric acid.
Nitrogen was determined by the phenol hypochlorite method (Weatherburn,
1967).
Phosphorus was determined after ashing, using ammonium vanado-molybdate
reagent.
Acetic acid was determined by gas liquid chromatography, on a Chromosorb
101 column.
Lactic acid was determined enzymatically (Noll, 1974).
The Chemical Oxygen Demand was determined by the procedure of the
American Public Health Association (1965).
Vinegar analyses were performed according to Pearson (1976).

RESUI~TS AND DISCUSSION

The results of the chemical analyses of Ghanaian pasteurised sweatings before and
after fermentation with distillers yeast, and naturally fermented sweatings from
Ghana and Dominica, are presented in Table 1.
The extremely high Chemical Oxygen Demand (COD) of the unfermented
sweatings is particularly striking and can be attributed to the high level of reducing

TABLE 1
ANALYSIS OF COCOA SWEAT1NGS BEFORE A N D AFTER FERMENTATION

Analysis Pasteurised sweatings Ghanaiant Dominican+


Before After jermented /ermented
fermentation fermentation* sweatings sweatings
pH 4.00 4.01 3.70 4.10
S.G. 20°C 1.042 1.010 1"005 1.001
Titratable acidity as anhydrous
citric acid, g 100ml-1 0.71 0.72 1.21
Volatile acidity as acetic
acid, g 100ml l 0-43 0.41 0.64
Acetic acid, g 100ml ~ 0-44 0.43 0.67 0.81
Ethanol, g 100 ml - 1 1.30 4-60 4.80 6.42
Total sugars, g 100ml ~ 7.34 0.80 0.35
Lactic acid, g 100ml 1 0.27 0.29 1.06
Total nitrogen, g 100ml 1 0.05 0.03 0.03
Total phosphorus, g 100ml ~ 0.01 0.01 0-01
Chemical Oxygen Demand, ppm 145000 49800~: 42000:1:
Soluble solids, g 100ml ~ 10.83 4-38 3.08
Ash content, g 100ml ~ 0.48 0.47 0.35

* Laboratory fermentation.
t Natural fermentation.
:~ After removal of ethanol by distillation.
No test.
228 M. R. ADAMS, J. DOUGAN, E. J. GLOSSOP, D. R. TWIDDY

sugars present. The concentration of ethanol found in all the fermented samples
falls within the range considered acceptable for economic recovery by distillation,
although the Ghanaian samples are at the lower end of this range (Ladisch & Dyck,
1979). The failure to observe any improvement in the yield of alcohol obtained when
the sweatings are pasteurised and inoculated with a pure culture of distiller's yeast
indicates that such additional processing would be unnecessary in any commercial
process. It is well known that alcohol distilleries are a major source of pollution in
the form of stillage. The COD of the ethanol-free residue produced after
fermentation and distillation of sweatings was still high but nonetheless a
substantial reduction in COD from the starting material was achieved.
There has been a resurgence of interest in recent years in the production of
fermentation ethanol for us'e as a fuel and chemical feedstock as well as in the well-
established role as potable spirit (Adams & Dougan, 1980, 1981). Cocoa sweatings
which are produced in large quantities in many countries represent a potentially
useful and cheap substrate for ethanol production.
An alternative use for sweatings which would eliminate the pollution problem
almost entirely would be the production of vinegar, since no intermediate
separation of alcohol is required in the process. Analytical data for two samples of
vinegar prepared from cocoa sweatings of different origin are presented in Table 2.
The Malaysian sample, which was produced using a natural inoculum of
Acetobacter spp, has a considerably higher acid content, probably reflecting a
higher content of ethanol after fermentation. The Ghanaian sample, which was
prepared using a pure culture of bacteria obtained from a commercial malt vinegar
brewery, shows a high conversion of ethanol into acetic acid, 1 litre of sweatings
yielding approximately 1 litre of 5 ~o acetic acid vinegar.
The analysis of the Ghanaian vinegar is closer to data reported for traditional
malt vinegars than is the Malaysian sample (Pearson, 1976). Both have considerably

TABLE 2
ANALYSISOF VINEGARDERIVEDFROM COCOASWEATINGS

Analysis Ghana* Malaysiat


Alcohol ( ~o w/v) 0.14 0.33
Alkaline oxidation value 176.4 241.6
Ash, mg ml - 1 5.1 4.2
Ester value 28.0 55.2
Formol titration, ml 0.1N alkali 1.55 1-90
Iodine value 1140 1850
Oxidation value 1486 2488
pH 3-4 3-2
Solids, ~ w/v 3-26 4-88
Total acidity (as acetic), g 100ml- 1 5.34 8.28
Volatile acidity (as acetic), g 100 m l - 1 4-99 7.62

* Laboratory acetification.
t Natural acetification.
USES OF COCOA SWEATINGS 229

h i g h e r p H a n d o x i d a t i o n values, w h i c h p r o b a b l y reflect the h i g h solids c o n t e n t o f


these p r o d u c t s , b u t t h e y s h o u l d be a c c e p t a b l e for c u l i n a r y use a n d as p i c k l i n g a g e n t s
for f o o d p r e s e r v a t i o n . A s d i l u t e s o l u t i o n s o f acetic acid t h e y also h a v e p o t e n t i a l as a
c h e a p local s o u r c e o f acid for latex c o a g u l a t i o n in r u b b e r p r o d u c t i o n .

ACKNOWLEDGEMENTS

T h e a u t h o r s are g r a t e f u l to M r R. S h e p h e r d , H a r r i s o n s a n d C r o s f i e l d ( M a l a y s i a ) ,
for the p r o v i s i o n o f the M a l a y s i a n v i n e g a r s a m p l e .

REFERENCES

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Volume 1, 325-33. ASIC, Paris.
ADAMS, M. R. & DOUGAN, J. (1981). Biological management of coffee processing wastes. Trop. Sci.,
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ADOMAKO,D. (1975). A review of researches into the commercial utilisation of cocoa by-products, with
particular reference to the prospects in Ghana. Cocoa Marketing Board. Newsletter No. 61, 12 20.
AGYEMAN,K. O-G., BEDIAKO,M. B. K. & OLDHAM,J. H. (1976). Pilot studies on collection of cocoa
sweatings. Ghana J. Agric. Sci., 9, 65.
A MERI('ANPUBLICHEALTHASSOCIATION(1965). Standard methodsjor the examination of water and water
wastes. (12th ed.), American Public Health Association, New York.
BORGES,J. M., GOMES,F. R. & PEREIRA,V DE P. (1978). A preliminary study of the standardisation of
cocoa jelly. Rev. Theabroma, 8(1), 3.
BROWNE,C. A. & ZERBAN,F. W. (1941). Physicalandchemicalmethods oJsugar analysis. (3rd ed.). John
Wiley & Sons, New York.
CAPUTI, A. & WRIGHT, D. (1969). Collaborative study of the determination of ethanol in wine by
chemical oxidation. J. Assoc. OJ]i Anal. Chem., 52(1), 85 8.
DOUGAN, J. (1980). Unpublished information.
KNAPP, W. (1937). Coeoajermentation. John Bale, Sons and Curnow Ltd, London.
LADISCH, M. R. & DYCK, K. (1979). Dehydration of ethanol: new approach gives positive energy
balance. Science, 205, 898 900.
MINIFIE, B. W. (1970). Chocolate cocoa and conJectionery. J & A Churchill, London, p. 13.
NOTE, F. (1974). In: Methods o]enzymatic analysis, Bergmeyer, H.U. (Ed.), Vol. 3, 1475- 9. Verlag
Chemic Weinheim/Academic Press, Inc., New York and London.
PEARSON, D. (1976). The chemical analysis oJfoods. Churchill Livingstone, London and New York.
WEATHERBURN,M. W. (1967). The phenol-hypochlorite reaction for determination of ammonia. Anal.
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