k c k c i i . S T (19941 Canirol or pnrr~clerirc rcduciion dunng chocohlc gnndino. .Iiunu/ Con/. 71 (5).

90-97
8 The Chemistry of Flavour Development
Blan,hard. l\I Y (1995) Thc g l x s rransiiion. 1,s m i u r c znd rigniiiciocc in ruad proccsring I n Phi in Chocolate*
Chemica1 Aiprrrr u/Faori Pru'rrriny (cd S T Bcckcii). pp 17 45 Chrpmin & Hrll. London
.
Bund. F C (1960) Cniihing i n d gnnding ulculiiions Brii Chcm Enf 6. 17s-391. 511-545
B o u n s . I & Brown. B D (1995) lnicriciions iAcciin~ microiiruciure. leriurc. i n d rheolog) o l chaola!c
c a n l e c i i o n c ~productr. In. IngrrJieni inirro<-iriin< E/lrrir on Food Q ~ a b , .(ed ~ A C C~onkar). P.S. Dimick and J.C. Hoskin
pp 411-528 Marce1 DLkker. Ncw i o r k
Fischcr. B I (1994) Puriirle rrzr d,riribtrun qieciian rhr<iiog.b a/ moiirn dark rh<iioiiiir, MSC iheiir.
Pcnnr)lr~,"r sizic Cniverr,,y
F n i i r h c . T (I994i Opiimimiion olinflucncing vrnrblcr in ihc cha-olaic rolliog procru Pzper givcn a i
Pruccrdingr Churoiuir Terhnoiog) IPPc 7-9 Dacmbcr. Colognc. Gemany ZDS. Sollngcn.
Hooobirk. C 119851 G l u r o u and laciose influence un chariciensiics o l chwalaic tiavarcd coaiingr
.I/MY/ C o n / . 65 i101 ?i-34.
Jackron. K 1199Jl Raiper I n I n d r r r r i ~ C i h o c o l ~ i i.tiunuJdiiure 2nd L ~c icd S T Beckeii). pp 255-250.
Chapmrn & Hall. Laoda" 8.1 Introdudion
Kaya. E.. Cho. H & tlogp. R 11993 Reagglomeraiion p h r n o m i n ~i n hncgnnding o l corl Min .Ii.~ruii
Pruc. 11. 17-13
Klimp.1. R R & blaolro?. W (1978) Chemical gnndins rid, far incrcn,ing ihroughpui in ihc r e i grinding
o l orer h d Eng Chrm Pror Drr ond Drr . 17. 513-521
The rnost notable attiibute oichncolate, which accounts ior iis universal appeal, is
Kusicr. W 0980) Tcchnologicil arpcrir o l iiyuor gnnding Paper given ai Prucerdingngr 34ih P.LiC4 its unique Ravour. The mix and balance o i the numerous cornpounds that conrribute
Produciion ConJfrrnrr. 22-24 A p n l Lanczsicr. PA pp 73-86 Penni?lvania hlinuficiuriog C a n l o - to the final Ravaur depend on genetics, environrnental condirions. harvesting and
cionen' ASSVEI~IIUO. H C T P ~ C ~ proc~ssing.With chocolate the chemical complenity o r Ravour developrnent is e n -
Kuricr. W (1984) Liquor grinding « i n u / ' Con/. M (81. 47-55 deni when ane realizes the numerous paramelers lhat may influence its developrnent.
Kuiicr W (1991) Pariiclc rizc fui", Con/. 71 (5). 57-60
Martin. R . & Siumpf. D M r19911 Prdrrrs O/ rejnrng rucchoride cr~riolsJuring foad piocrrring CS
11s cornpleriry is equally obvious when considering that, even today. this desirable
Paicni 5.080.911 Ravour has not been duplicated by the Ravour chemist.
McGcilc?. R L: (19611 hfcchaoeal p a c k ~ o o orphcncalprriidcs
l I Am Cerumii S o c . 44(lO). 513-522 Among numerous iactors, the organoleptic properties of chocolate may be
hlong~=.C i19911 Poriirir skr durribuiian a f i c u ihr rhr.oiogi ond rrmori aririhurir o/miIk rhoroiarr dependent on che varieiy of ihe cacao used as siarring rnarenal in manufacture. Far
PhD ihcrir. Pcnnsylvinli Smlc Cnivcrriiy example, the Criollo- and Trinirario-based varieties are known to have fine chocolate
hiedick. E A ,19941 Pariicle rzze rcduciion I n indwrriiil Chucolurr .Ilunufiriurr ond L l r . (ed S T
Bcckelr). pp 8J-101. Chapman & Hall. London
Ravour. oiten described as a mild nutiy and a full chocolate Ravour. respectively. and
Olingcr. P > I (1994) N e w opiionr lor iucroic lrec chocolari .tiunu/ Con/. 71 (1). 77-84 are considered 'fine-grade' cocoa. The 'bulk' cocoas, which make up the vast rnajor-
Pangburn, R 41 k Ka?rrako. A (1981) T i n i c i o u r u a l ~ ~ ~ 0 5 succ~n~ss 1 1 ~ . and flavor in chuculiic i ~ yo i the world's production, are irorn Forastero varirties. Although they are of
dcrurlr J Terr S i u d l?.141 -150 good qualiiy, they have less fine chocolare Ravour when carnpared [o the Criollo
Peier. T (1994) Pnriirlc rzzc riduiiion a i i h ihc tuo-iirge rcfining r)r!cm Prpcr giren ri Pri>cec~dingz type (see Chaprers 2 and 18). Formulations ultilizing a single bean vanety. o r rhose
Choroioir Techn<iiuqv 1994. 7-9 Doembrr. Cologne. G e m a n r ZDS. Sulingen
Rumpl: H (1962) Thr iirength o l g r ~ n c l ar n d agglomcraic>. In. .Agglumi~riiiionicd W A Kncpperl.
uning blends, ma? thereiore haie dramatic variirions in flavaur. Cultivarion and
pp 319-413 Wilcy. Ncu Yurk. husbandry practices may also havr an irnpacr on the Ravour. The limited time spent
Slhmicder. R L & Kccnc?. P G (1980) Char~cienraiionrnd qu.inciiiwiion a l ri,irch in cocor brans i n d b) ~nbesrigaiorson this subject indicaies rhat this is a minor influence; however, with
chwoiiic pruducii J FuudSc.!. i 5 (3). 555-561 rhe idvent o i biotechnology, researchers can characterize cocoa beans al their mosr
51 Juhn. J F. i!o/ (1995) Reducrdloi iun/<criuncri producrr u n d p r u r r i r . C'S Pnient 5.464.fA9. basic level. by genotype. Molecular mipping and fingerpnntin: techniques in cornbi-
Suddurh. R D (19934 A generslized mi*lcl lo predici ihc m a ~ i m u mpacking Irzciion 2nd ibe i t r o r i i ) or
roluiianr u i i h iurpendcd pariicier I I .Appi P v l m Si-, , a. 25-36,
nation wiih srnsory analysis haie pravided researchers with a beiier undersranding
Sudduih R D 0 9 9 l b ) A new m e i h d i o predici ihc maximum packing lraclion 2nd ihc iiworii) or o i ths inRuence of iree genetics on Ravour. In 1994 Matlick described an ACRI
raluiiunr wiih a iirc disiribuiion o l iurprndcd p;iriiclcs Il J Appi Pohm S i i . UI. 37-51 (.\merican Cocoa Research Insriture) sponsored project that indicated thir certain
Sudduih. R D (1993~1A gencralized modcl to prcdici ihc i i w o r i i ? olroluiionr a i i h r ~ i p c n d c dp~riiclcs hybrids produce significantly inferior chocolare flaiour. Sis rnajor chocolare
I l 1 Effecis o l pariicle inieraciion snd p r n i c k .izc di5inbuiion. J. Appi P u b m S c i . YI 123-147 rnanuiaciuiers followed ihe sarne Ravour raiing procedure to evaluare hybrids and
Tanginpongkul. S (19933 BrriJro$r mr.ihunrrm m uurogrnuur grinding PhD iheri,. Prnni?liania S r ~ i e
cniversii~
their parcnts. which had originated frorn the Cocoa Research Station in Costa Ricd
Windhab E J i 19951 Rhcalos~in lood prwcuing In. Phiricu-Chrmic~i I r p r i r r a i Fuad Procirring (CATIE). The sludy rcsulred in a ranking o i cach genaiype based on i l s Ravour
(ed S T B c c ~ ~ I I )pp.80.
. 115 Chapman & Hall. London.
Windhab. EJ (199-1 Siruriuri-rhcology reiiiionshipi in cha-oliie prweiring Paper giuen al Prarridingr
o / m Inrrrnori<indi$mposimon Con/rrriunrri Sciince. 11-12 Apnl. Iniicrrii? Pdrk. PA. pp IOJ 1 2 6
.Technical Caniribuiion h'o 2696 or ihc Saulh Carolina A ~ ~ c u l r u Erperimcni r~l Sialion.
Pcnn7ylirnia Sirlc Uniwrriiy, Pcnnrylvsnia.
Clcrnson L'niiersii) T ~ c h n i c a l Contribuiion No 7658 of ihe P c n n i ! l v ~ n i ~Siaic Univrrsiiy
-\pnculiural Erpenmcni Siarion

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 ihe Chemirtryrif Fiamur Development in Chocolale 141

temperarure, atmosphere and selrcrrd compounds in thc pulp during lermeniation is
illustrated in Fig. 8.1 (Lopez. 1986). Tablr 8 1 illustrares the pH. titrarable acidiry,
acetic and lactic acid concentrarions. fermentation index and cut tesr scores for
cocoa beans from differenr countries o l o r i g n (Jinap & Dimick. 1990). Cocoa beans
with high pH (5.5-5.8) were considered under-fermenred as indicated by the l o u
fermentation index and cui [est scare At che same rime. those beans a i t h low pU
(4,75-5.19) were well lermentcd. Fcmenration techniques to reduce acid Ravour and
maximize chocolate flavour are in prxtice (Duncan, 1991).
The problcrns oldefining the flavour mechanisms thai occur during fermeniation
are difficult and as yer have not been delinitively elaborated, in part because of the
reacrions 1s ihe increase in fructore as compared to glucose after approximaieiy
2 d3ys 01 fermentation. The increase in srarch concrnrrarion during lermentation
(1%) might imply [hai glucose originating lrom hydrolyrrd sucrose is urilized to
produce stirch (Reineccius rl al., 1972.1). Fructose, less uiilizrd because it requires
conLersion. uould then be found in higher concenirationi compared to glucose.
Houevcr. ir h39 been suggested that sugars are available from the fermenting pulp or
other sugar sources. The reason lor this change has noi been derermined. although it
could be ver) imporrant in relation ro the establishmenr of rcducing suears for the
inreraction a i t h amino compounds i n carbonyl amino reactions. Thus. the sugars
present in ihe cor?ledon. associated shell and dried pulp are vcry imporiant flavour
~ ~

many variations in lermenration methods. There are undoubtedly as many dtfferent
methods of fermentation as there are counrries that produce cocoa beanr. It can bc
said ihat the beans undergo an anaerobic hydrol?tic phase. followed intermittcntly
by an aerobic phase. The timing, sequence of events and degree o i hydrolyris and
oxidation may be highly variable from fermenration to fermentation. The presence
ond concenrration of che many flavour precursors that occur during this stage ars
dependent on enzymatic mechanisms (Lopez & Dimick. 1991) No1 only are flavour
precursors produced, but colour changes also occur The hydrolysis of the poly-
phenol compounds by the glycosidases (Lopcz. 1986) results in bleaching and at the
same rime influencrs the Aavour (Wadsworth, 1955; Rohan. 1958).
In early fermentation rhe mojor saccharide is sucrose: however, i t is soon
hydrolysed into glucose and fructose as fermentation progresses (Knapp, 1937;
Reineccius er al.. 1972a; Berbert. 1978). One interesting point during hydrolysis
precursors.
The major nirrogen-eonraining precursors lormed during the anaerobic phase of
fermentation are the numerous amino acids and peptides (de Witt, 1957; Roelofsen,
1958: Rohan. 1958: Zak & Kseney, 1976; Timbie & Keeney, 1977). Theie amino
compounds are available lor rhe non-oxidaiive carbonyl-amino condensaiion reac-
tions that occur dunng ihis and later heating phases, ruch ar drying, roasring and
grinding. Although some of thc protein is degraded to flavour precursors, rhe punty
of the remaining protein decreases because of polyphenolic protein interaciions.
During che aerobic phare, many oxygen-mediated reactions occur, one of impor-
tante being that of the oxidation of proiein-polyphenol complexes formed during
the anaerobic phase (Forsyrh & Quesnel, 1963). There mechanisms reduce astrin-
gency and bitrerners as the oxidired polyphenols can complex with proteins and
peptides, modifying furiher protein degradation rractionr (Roelofsen, 1958).

Table 8 1 lumrnaryof acidc characterirticr and degree o f fermentaton o1 cocoa beanr

irom dfferent argin countrier (linap & Dimck.1990) Reprinted fiam I Food Sci.. 55 (21, 8.3 Drying
547-550. Copyright e by ln5iirute af Faod Technologrts.
Folloaiiig the fermenration procesr the k ~ n are s dried and this is also instrumental
Paramctrrr ViIucs Counrries o l origin in flavour prrcursor development. Indicators of good drying practices. relating ro
flavour quality of the beani, aie good brown colour and low asiringency and
LowpH(1 75-5.19) bitterness Frrrdom from OR-flavours, such as excessive acidity and hammy\smoky
Tirraiablc icidiiy O 17-020 blalaysma, Bvml,
Accric acid 0.52-081e l00g Solomon lilandr flavour, is also indicative o f proper drying. Flavour assessmentr ofcocoa beanr dried
Licric acid 027-050g Ioog using diiierent mrihods. i e . sun drying, air-blowing, rhade dryin- and oven drying,
Femeniiiion indcr 081-1 98 demonstrated t h ~ ihei sun-dried samples rated higher in chocolate flavour devel-
Cui icst rcarc 329-5?3 opmenr and had feuer off.notes (Selamat e i al., 1991).
Mediwn pH (5 20-5.49)
It is during the drying phase of cocoa curing that the characierislic brown colour
Titratablc acidi," 0.12-O I 5 Camcroon. Gibon. ofchocolate develops. Major oxidizing reactions occur wiih polyphenols, catalysed
Accric acid 0.A-0 568 1 0 0 ~ Ghnna, Nigeria. Ivoq Coisr, by rhe enryme polyphenol oxidase. The death of ihe bean, wiih loss a i membrane
Laciic acid 0.21-0298 l00g Indonesia, Dominican Republic integriry. allows previously restricted enzymatic reacrions and resulrs in brown
Femcniaiion nder 064-178 colour iormation. Modern technology has changed the dependence on ihe sun for
Cui ieri scorc 267-153 drying and allows arrificial or mechanical drying processcs uhich are not uithout
H~ahpH (550-5 80) drawbacks. With mechanical dricrs. uhere high temperatures may be used. case-
Tirraublc aridi,? 0.11-0.13 Ecuador. Venezuela. hardenine.mav. result. Excessive hear and rapid drying may not allow for adequare
Acetir arid O.4&0.55 g. l W g Gualernnla loss of the volarile acids, e g . acetic acid, and therefore have a derrimental effect on
Lacric arid 0.21-030g IOOg oualitv.
7 - ~, There also mav , be rituations uhere rhe water activitv within the bean is such
Fementarian indrr
Cur resi wore
0.49-0 92
213-308 that the drying process is merely a continuarion of the fermentation process.
many reactions can proceed. A high Icvcl o i water aciiviry, as a result of incomplete ,T
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