Eur Food Res Technol (2005) 221:434438 DOI 10.

1007/s00217-005-1196-2

ORIGINAL PAPER

Monica Anese Lara Manzocco Enrico Maltini

Effect of coffee physical structure on volatile release

Received: 19 November 2004 / Revised: 14 March 2005 / Published online: 21 July 2005  Springer-Verlag 2005

Abstract The mechanisms of volatile release from soluble coffee powders with different roasting degrees were studied. The presence of volatiles in the headspace during coffee humidification was analyzed by gas chromatography. Small amounts of volatiles were observed at low water activities (aw), independently from the roasting degree; as the aw increased headspace volatiles rose and then decreased as the moisture further increased. The changes in aw and volatiles went along with the changes of coffee structure from a free-flowing powder to a sticky viscous fluid. The mechanism of volatiles release was controlled by both kinetic and thermodynamic factors. The former prevailed at low aw in glassy systems; while the latter became important at high aw when, due to increased mobility, equilibrium conditions were approached. Modified state diagrams were used to predict the critical temperature and aw at which structural collapse and volatile release occurred. As far as equilibrium condition was achieved, coffee volatiles were partially readsorbed in the liquid phase. Keywords Coffee powder Volatile release Physical structure Phase transitions

Introduction
Flavor is one of the most important attributes of food quality and acceptability. The partition of volatile components between the gas phase and food is relevant to the resulting quality [1]. However, as partitioning phenomenon is mainly controlled by interactions between volatile and nonvolatile components, control or prediction of flavor release can be difficult [2]. For instance, manuM. Anese ()) L. Manzocco E. Maltini Dipartimento di Scienze degli Alimenti, University of Udine, Via Marangoni 97, 33100 Udine, Italy e-mail: monica.anese@uniud.it Tel.: +39-0432-590711 Fax: +39-0432-590719

facturing and stabilization processes, as well as domestic manipulation, may often cause modification in the flavor partition thus affecting aroma intensity or profile [1, 3, 4]. Although not all volatiles are flavor components, an understanding of the mechanisms involved in volatile retention and release by a food matrix may be required for a better control of sensory quality of foodstuffs [5]. Many literature studies deal with the volatile retention in low moisture food matrices [610]. The high degree of volatile retention in dehydrated foods, particularly in freeze-dried products, contrasts with the behavior expected for organic compounds, considering their relatively high volatility compared to that of water [5, 7, 10 18]. This deviation from the expected behavior has been taken, since the earliest investigations, as a physically and structurally based phenomenon [1922]. According to these theories, volatile compounds are entrapped into the dehydrated matrix and are released during moistening due to structural collapse of the matrix itself. In the end of the 1980s, by introducing the concept of glass transition, it has been assumed that dehydrated foods can be considered as amorphous, metastable solids. When the residual moisture is low enough, amorphous materials may exist in a glassy state at room temperature. In these conditions physical changes and related phenomena depend on kinetic rather than thermodynamic mechanisms, and their occurrence can be predicted with reference to the glass transition temperature (Tg) [23, 24]. According to this interpretation, volatiles are entrapped in the amorphous glass, where diffusion is very low. Plasticization by absorption of water may cause the depression of Tg below room temperature, and hence the glassrubber transition of the matrix. In these conditions the structural change of the matrix may allow initial collapse to occur and volatiles to be released [2528]. Following the hypothesis mentioned above, the objective of the present work was to investigate on the role of structure transitions in the volatile release from instant coffee, a well-known example of food matrix characterized by high volatile retention.

435

Materials and methods

Coffee powders Light-, medium-, and dark-roasted soluble coffee powders were obtained by extraction and spray-drying from a same blend. According to the supplier (Nestl Research Centre of Lausanne), the powders were characterized by color test Neuhaus (CTN) values of 110, 85, and 60, and weight losses of 14.2, 16.2, and 18.9%, respectively for the light, medium and dark types. Sample preparation Aliquots of 25 g of each soluble coffee were solubilized with 25 g of deionized water, freeze-dried (Mini Fast mod. 1700, Edwards Alto Vuoto Spa, Trezzano sul Naviglio, Milano, Italy) and stored under P2O5 for few days before further manipulations. The same procedure was followed for a light-roasted coffee sample added with 2% (w/w) ethanol (Carlo Erba, Milano, Italy) before freezedrying. a. Weighed vials (10 mL capacity) containing approximately 1 g of freeze-dried powders were equilibrated in vacuum dessicators containing saturated salt solutions (Carlo Erba, Milano, Italy), having equilibrium relative humidities (RH) ranging from 11 to 94%, and maintained at 25 C. After 1 week, equilibrium conditions were reached and vials were hermetically closed with butyl septa and metallic caps. b. About 2 g of the freeze-dried light-roasted coffee containing ethanol (2% w/w) were introduced in 300 ml-capacity glass flasks over saturated CuCl2 (68% RH) solutions. Analysis was performed over the equilibrium time of 120 h. Headspace gas-chromatographic analysis Analyses were performed on samples conditioned at 25 C in a temperature-controlled water bath by using a Fisons gas-chromatograph (HRGC MEGA 2 series, Fisons Instruments, Milano, Italy), equipped with an automatic sampler and a flame ionization detector (Carlo Erba HS 250, Carlo Erba Strumentazioni, Milano, Italy). A 2 mm2 mm i.d. glass-packed column filled with Carbopack 20 M 80/100 mesh (Waters Association, Framingham, Massachusetts, USA) was used. The operating conditions were as follows: column temperature, 80 C; detector oven temperature, 200 C; injector temperature, 200 C; carrier gas (nitrogen) flow rate, 35 mL/min. The headspace volume injected was 0.5 mL using a precision sampling syringe (Dynatech Precision Sampling, Baton Rouge, Louisiana, USA), provided with a pressure lock and a gas volume capacity of 00.5 mL. The chromatograms were analyzed using a ChromCard for Windows software (Carlo Erba Instruments, Milano, Italy). Ethanol vapor pressure (Pe) was calculated from the chromatographic response of the ethanol peak area by using the Kolb equation [29]:   A P Po o A where Po is the vapor pressure of pure ethanol, equal to 7.45 kPa at 25 C; A is the ethanol peak area; Ao is the pure ethanol peak area. Calorimetric analysis Calorimetric measurements were made by means of a TA 4000 differential scanning calorimeter (Mettler Toledo, Greinfensee, Switzerland), equipped with a DSC 30 low-temperature measuring cell and connected to a Graph Ware software (TA 72.2/.5, Switzerland). Heat flow was calibrated using indium (heat of fusion 28.45 J/g). Temperature was calibrated with n-butyl alcohol (m.p.

89.5 C), water (m.p. 0 C) and indium (m.p. 156.6 C). Amounts of about 10 mg of coffee samples, were placed into 40 mL aluminum DCS pans closed with pressure sealing. An empty aluminum pan was used as a reference. The glass transition (onset Tg) temperatures of the anhydrous powders were measured by heating from 100 to 200 C at 10 C/min. The transition temperatures of the coffeewater mixtures were determined after rapid cooling of the samples to 100 C, heating at a scanning rate of 10 C/min up to the onset of the melting endotherm, re-cooling at 100 C and scanning to 200 C at 10 C/min. Total solid content Total solid content was determined according to AOAC methodology [30]. Sorption isotherms Sorption isotherms were measured by accurately weighed samples in vacuum dessicators containing saturated salt solutions with constant water vapor pressure until constant weight [31]. Measurements were carried out at 25 C. Saturated salt solutions with RH between 11 and 94% were used. Water activity Water activity (aw) was determined by means of a dew-point measuring instrument (AQUA LAB, Decagon, Pullman, WA, USA) at 25 C. Microscopic analysis Coffee samples were analyzed by means of optical microscopy (Wild Makroskop, M420, Switzerland) with image magnification equal to 20. Images were captured with a video camera (Color Video Camera Head, JVC, Model TK 1280Z, Japan), and elaborated using the software Adobe Photoshop (6.0, Adobe Systems Inc., 2000). Data analysis The results reported in this work are the average of at least three determinations and the coefficients of variation, calculated as the percentage ratio between the standard deviation and the mean value, were less than 7% for calorimetric analyses, less than 5% for gas-chromatographic and total solid content determinations and less than 3% for water activity. The significance of the differences among means was determined using the TukeyKrammer test [32]. Means were considered to be significantly different at P<0.05. The glass transition temperatures of samples equilibrated at different RH were fitted according to the Gordon-Taylor Eq. (1) [33] by using a Table Curve 2D software (SPSS, Chicago): Tg w1 Tg1 kw2 Tg2 w1 kw2 1

where w1 and w2 are the weight fractions for coffee and water, respectively, Tg1 and Tg2 are the glass transition temperatures of the amorphous coffee and water, respectively and k is a constant. The Tg of water was taken at 136 C [34].

436

Results and discussion

Figure 1 shows the equilibrium headspace volatile area, measured at 25 C, of light-, medium- and dark-roasted coffees as a function of aw. As expected, the presence of volatiles in the headspace of coffees increased with the increasing of the roasting degree [35]. At both low and

Fig. 1 Total peak area of headspace volatile compounds of light('), medium- (n) and dark-roasted (l) soluble coffees as a function of aw

high aw, the headspace area of volatile compounds was very low, whereas the peak areas were highest at intermediate aw. The aw associated with the increase of volatiles in the headspace was in the range of 0.250.35 for the light- and medium-roasted coffees, while a high volatile area for the dark-roasted one was observed up to an aw of about 0.7. Thus, the presence of volatiles in the headspace showed a bell-shaped behavior for all the coffee samples. High volatile retention at low aw values was also observed by Flink and Karel [7] on aqueous model systems containing soluble carbohydrates and organic volatiles. According to these authors, in such systems volatile compounds would be entrapped in microregions formed by carbohydratecarbohydrate hydrogen bonds. A bell-shaped behavior was also reported by Gunning et al. [9], although their study was more focused on the effect of water content on volatile release. In coffee samples, the changes in headspace partition of volatiles were associated with visible changes in the physical structure of the powders (Fig. 2). By examining the images of the light-roasted coffee samples equilibrated at different aw (Fig. 2), it is possible to have an idea of their physical structure. At very low aw the structure was that of a free-flowing powder. At aw of 0.33, where the headspace area of volatile compounds was

Fig. 2 Photographs (20) of light-roasted coffee samples having different aw (A, aw=0.05; B, aw=0.33; C, aw=0.48; D, aw=0.70)

437 Table 1 Onset and endset of the glass transition temperature (Tg),   glass transition temperature of the maximally freeze-concentrated solute T 0g for light-, medium- and dark-roasted coffee samples   Roasting Tg (onset) Tg (endset) T 0g (C) degree (C) (C) Light Medium Dark 66 67 65 83 78 80 39 39 39

Fig. 3 Modified state diagram of light-roasted coffee

high, the powder structure could be described as a hydrated amorphous mass, probably because of the initial formation of liquid bridges between the coffee particles [36]. As the aw value further increased (aw>0.44), with a corresponding decrease of peak area, the coffee matrix turned into a sticky and fully collapsed structure. As known, collapse or structural sinking is a time dependent physical change, which occurs when viscosity is reduced to a value at which the porous matrix cannot sustain its own weight against gravity [37, 38]. As mentioned above, volatile compounds may be released upon collapse. However, in the latest stage of collapse a drastic decrease in porosity occurs and diffusion of the residual volatiles may become strongly hindered. In any given system, the temperature at which collapse may occur depends on water content and solute nature: it decreases with the increase of water content and the decrease of solute average molecular weight [37]. In structurally simple systems (e.g., sugar solutions) the collapse temperature coincides with Tg; in more complex systems, containing suspended matter, or viscosant components (hydrocolloids, starch, etc.), or when an insoluble cellular matrix is present, the apparent collapse temperature may be higher than Tg. Figure 3 shows a modified state diagram relative to the light-roasted coffee. In principle, modified state diagrams, where Tg and water content are plotted against aw, allow the aw/temperature conditions at which the system might undergo glass transition to be predicted [39]. According to Fig. 3, at room temperature (e.g., 25 C) the soluble coffee powder is in a glassy state at aw lower than about 0.35; over that critical value, the transition to a viscous rubbery state may allow matrix collapse to initiate and volatiles to be released. Such transition may thus be associated to an increase of both temperature and/or water content. By contrast, storage of coffee at lower temperatures would allow collapse and thus volatile release to occur at higher water content and aw. Similar diagrams (not shown) were obtained for the medium- and darkroasted coffees. In the experimental conditions, coffees Tg (Table 1) as well as water sorption data (data not shown for medium- and dark-roasted coffees) were not significantly affected by the roasting degree (P>0.05), although the amount of volatiles was much higher in the

Fig. 4 Total peak area of headspace volatile compounds of lightroasted soluble coffee added with 2% (w/w) ethanol as a function of equilibration time to 68% RH. aw values at corresponding equilibration times are also reported

dark-roasted coffee. Taking into account that coffee powder was only slightly hydrated at the moment of maximum amount of volatiles in the headspace (Fig. 2) and that the glass transition spanned over a rather large temperature range (Table 1), it is likely that most of the volatile compounds are released in the first stage of collapse, just above the onset of the glass transition. The decrease of volatiles after the maximum requires an explanation. In principle it could be hypothesized that at high aw the kinetics of volatile release is slower than that of collapse, and volatiles can no more escape from a fully collapsed matrix. Alternatively, a volatile re-adsorption by the salt solution and/or the product itself should be envisaged. To check the above hypothesis, the kinetics of volatile release during equilibration to a constant 68% RH was evaluated on a light-roasted coffee sample added with 2% (w/w) ethanol, which was shown to not affect the Tg of the coffee sample. Samples were analyzed for volatiles and aw at time intervals during equilibration. Figure 4 shows the nonequilibrium headspace total peak area as a function of time. Again, a bell-shaped curve, with a maximum at about 0.44 followed by a decrease was observed, which also in this case was associated to a sticky and collapsed structure. This behavior confirms that sufficiently hydrated sample and/or salt saturated solutions are able to partially re-adsorb volatiles, when the kinetic effect of the matrix structure becomes less important due to the increased mobility. To evaluate the matrix effect, the behavior of coffee samples added with 2% (w/w) ethanol and equilibrated at different aw was compared with the results of a similar

438 9. Gunning YM, Gunning PA, Kemsley EK, Parker R, Ring SG, Wilson RH, Blake A (1999) J Agric Food Chem 47:51985205 10. Rifa MK, Voilley A (1991) J Food Sci Technol 28:135137 11. Lerici CR (1976) Rivista Scientifica di Tecnologia, Alimentazione e Nutrizione Umana 6:2731 12. Aguilera JM (2000) Structure-properties relationships in foods. In: Lozano L, Anon C, Parada E, Barbosa G (eds) Trends in Food Engineering. Technomics, Lancaster, PA, pp 114 13. Blake A (1994) Int Food Ingredient 3:3034 14. Omatete OO, King CJ (1978) J Food Technol 13:265280 15. Rosenberg M, Kopelman IJ, Talmon Y (1990) J Agri Food Chem 38:12881294 16. Thijssen HAC (1971) J Appl Chem Biotechnol 21:372377 17. Voilley A (1995) Flavor encapsulation. Influence of encapsulation media on aroma retention during drying. In: Risch SJ, Reineccius GA (eds) Encapsulation and Controlled Release of Food Ingredients. American Chemical Society, Washington, DC, pp 169179 18. Whorton C (1995) Factors affecting volatile release from encapsulation matrices. In: Risch SJ, Reineccius GA (eds) Encapsulation and Controlled Release of Food Ingredients. American Chemical Society, Washington, DC, pp 134142 19. Chirife J, Karel M, Flink J (1973) J Food Sci 38:671674 20. Flink J (1975) The retention of volatile components during freeze-drying: a structurally based mechanism. In: Goldblith SA, Rey L, Rothmayr WW (eds) Freeze Drying and Advanced Food Technology. Academic Press Inc., London, pp 7988 21. To EC, Flink JM (1978) J Food Technol 13:567581 22. To EC, Flink JM (1978) J Food Technol 13:583594 23. Levine H, Slade L (1986) Carb Polym 6:213244 24. Levine H, Slade L (1988) Cryo-Lett 9:2163 25. Labrousse S, Roos Y, Karel M (1992) Science des Aliments 12:757769 26. Levi G, Karel M (1995) J Food Eng 24:113 27. Shimada Y, Roos Y, Karel M (1991) J Agric Food Chem 39:637641 28. Whorton C, Reineccius GA (1995) Evaluation of the mechanisms associated with the release of encapsulatated flavor from maltodextrin matrices. In: Risch SJ, Reineccius GA (eds) Encapsulation and Controlled Release of Food Ingredients. American Chemical Society, Washington, DC, pp 143160 29. Lerici CR, Nicoli MC, Manzocco L (1996) Industrie Alimentari 35:1313 30. AOAC (1995) Official Methods of Analysis 16th ed. Associations of Official Analytical Chemists International, Arlington, VA. Chap.42 31. Gal S (1975) Recent advances in techniques for the determination of sorption isotherms. In: Duckworth RB (ed) Water Relations in Foods. Academic Press, London, pp 139154 32. SAS (1999) JMP 3.2.5. SAS Institute Inc., Cary, NC 33. Gordon M, Taylor JS (1952) J Appl Chem 2:493500 34. Johari GP, Hallbrucker A, Mayer E (1987) Nature 330:552553 35. Grosh W (2001) Chemistry III: volatile compounds. In: Clarke RJ, Vitzthum OG (eds) Coffee Recent Developments. Blackwell Science Ltd., Oxford, UK, pp 6889 36. Peleg M (1983) Physical characteristic of food powders. In: Peleg M, Bagley EB (eds) Physical Properties of Foods. AVI Publishing Company Inc., Westport, CT, pp 293323 37. Tsourouflis S, Flink JM, Karel M (1976) J Sci Food Agric 27:509519 38. Levi G, Karel M (1995) Food Res Int 28:145151 39. Roos YH (1995) Phase Transitions in Foods. Academic Press, New York

Fig. 5 Ethanol vapor pressure as a function of aw of ethanol-containing light-roasted coffee (') and water-glycerol systems (n)

experiment, taken from Lerici et al. [29], on a water glycerolethanol system. Figure 5 shows that, in contrast to the bell-shaped behavior of the coffee-based system, the ethanol vapor pressure over the waterglycerol system linearly decreased as the aw increased. Actually, the glycerolwater system is a low viscosity liquid where thermodynamic equilibrium spans over the entire aw range and liquidvapor partition obeys to the Raoults law. In light of these results, it can be concluded that, at aw values lower than the critical one, the coffee volatile release in the headspace is under kinetic control. On the contrary, when coffee samples have passed through and overcome a critical aw, the kinetic constraints are progressively reduced and the system tends to the attainment of a thermodynamic equilibrium. The latter implies volatile partition between liquid and vapor phases according to the Raoults law.
Acknowledgements Nestl Research Centre of Lausanne is thanked for providing the coffee samples

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