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Accepted Manuscript

Beverage Emulsions: Recent Developments in Formulation, Production, and
Daniel T. Piorkowski, David Julian McClements






To appear in:

Food Hydrocolloids

Received Date: 13 May 2013
Revised Date:

8 July 2013

Accepted Date: 9 July 2013

Please cite this article as: Piorkowski, D.T., McClements, D.J., Beverage Emulsions: Recent
Developments in Formulation, Production, and applications, Food Hydrocolloids (2013), doi: 10.1016/
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Graphical Abstract
PRODUCTION, AND APPLICATIONS” by D.T. Piorkowski and D.J. McClements




Food Hydrocolloids

The article provides an overview of recent research on the formation, stability, and




properties of beverage emulsions.







Daniel T. Piorkowski and David Julian McClements1



Department of Food Science, University of Massachusetts, Amherst, MA 01003








Journal: Food Hydrocolloids


Submitted: March 2013


Revised: July 2013







Department of Food Science, University of Massachusetts, Amherst, MA 01003,, 413 545 1019

as well as a 31 discussion of the functional ingredients used to formulate these systems. emulsions. we discuss recent 35 developments in the soft drinks area. nutraceuticals. A brief overview of the various high and low 30 energy methods available for preparing this type of beverage emulsions is given. and thickening agents. 32 emulsifiers. RI PT 26 This review article focuses on the utilization of emulsion science and technology for the 29 fabrication of soft drinks by the beverage industry. with special focus on their influence on product stability. soft drinks. flavors. including fortification with vitamins. Finally. including oil phases. The influence of 33 droplet characteristics on the physicochemical and sensory properties of beverage emulsions is 34 reviewed. nanoemulsions AC C 38 M AN U SC 28 . weighting agents. and “all-natural” products. reduced calorie 36 beverages. 37 EP TE D Keywords: beverages.ACCEPTED MANUSCRIPT 2 25 27 Abstract Soft drinks are one of the most widely consumed and profitable beverages in the world. ripening inhibitors.

exposure to light and oxygen. such as temperature fluctuations. such as clouding agents. buffer type. molds or 66 bacteria). exposure to mechanical forces (such as stirring. McClements & Li. Cola is the top soft drink flavor currently consumed in the United States. a microemulsion. McClements & Li.. soft drinks are one of the most widely consumed and profitable beverages (Table RI PT 40 1). 2007. oil-soluble 46 vitamins. and vibrations). and biological attributes to the final product. ionic strength. and oil-soluble antimicrobials. All three of these soft drink flavors contain hydrophobic 44 citrus compounds extracted from fruit peels. Decker. nanoemulsion. 65 ingredient interactions). . sensory. 52 2011. The non-polar character of flavor oils and other 47 hydrophobic ingredients means that these ingredients cannot simply be dispersed directly into an 48 aqueous phase – they would rapidly coalesce and separate through gravitational forces leading to 49 a layer of oil on top of the product (Given. or emulsion (McClements. weighting agents. 2010). e. 2009). reliable and inexpensive manufacturing methods that are easily implemented. storage. & Weiss. variations in aqueous phase composition (such as pH. Introduction Globally. flow through a pipe. A 54 number of desirable attributes of colloidal delivery systems suitable for application in beverage 55 products are highlighted below (McClements. Instead they first have to be converted into a 50 colloidal dispersion consisting of flavor molecules encapsulated within small particles suspended 51 within an aqueous medium. transport and utilization. nutraceuticals. the delivery systems should be fabricated using robust. 59 60 TE D • EP 56 SC 42 that a product may experience during its production.g. and exposure to microorganisms (such as yeasts. the delivery systems should be fabricated entirely from “label friendly” food-grade ingredients that are economic and easy to handle. 2010): M AN U 57 58 • 62 63 64 Fabrication: Ideally. These colloidal delivery systems must be carefully designed to 53 provide desirable physicochemical. • Stability: The delivery systems should be designed to withstand all of the stresses AC C 61 Composition: Ideally.ACCEPTED MANUSCRIPT 3 39 41 1. Soft drinks may also contain a variety of other 45 hydrophobic components. with lemon-lime 43 and orange being the second and third.

which is desirable for soft drinks that should be clear. 87 the formation of microemulsions usually requires relatively high levels of synthetic surfactants 88 and sometimes the use of cosurfactants/cosolvents. oil-soluble vitamins. taste. and production of emulsion-based delivery systems suitable for utilization within the beverage 75 industry. or flavor profile (aroma. McClements & Rao. McClements & Rao.ACCEPTED MANUSCRIPT 4 • 67 Physicochemical and sensory properties: The delivery system should not adversely 68 affect the optical properties. Emulsion Science and Technology in the Beverage Industry M AN U 77 SC 74 Hydrophobic components (such as flavor oils. Each of 81 these colloidal dispersions has particular benefits and limitations for the encapsulation of 82 hydrophobic compounds. and 89 labeling reasons. 76 2. and nutraceuticals) can be incorporated into a variety of different colloidal delivery systems suitable 79 for application within beverage products (McClements. nanoemulsions. Microemulsions may also become thermodynamically unstable if 90 environmental conditions are altered (such as temperature or composition). and mouthfeel) 69 of the beverage product into which it is incorporated. 95 Emulsion systems must therefore be carefully designed to inhibit these instability mechanisms . 72 or nutraceuticals. et al. with 80 the most common being microemulsions. and emulsions (Figure 1). rheology. Microemulsions are thermodynamically stable systems under a 83 specific set of environmental conditions (e. Biological activity: The delivery system should not adversely affect the biological RI PT • 70 71 activity of any encapsulated bioactive components. On the other hand. and therefore tend to breakdown during storage through a 93 variety of instability mechanisms (Figure 2). vitamins. 2012. 2007. which can be undesirable for cost. 73 This review article provides an overview of the current status of the design. 94 coalescence and Ostwald ripening (McClements. formulation. such as antimicrobials.. and are therefore 84 easy to fabricate (often by simple mixing) and tend to have good long-term stability. 85 Microemulsions typically contain very small particles (r < 25 nm) and therefore tend to be 86 optically transparent. flocculation. composition and temperature). EP AC C 91 TE D 78 Conventional emulsions (r > 100 nm) and nanoemulsions (r < 100 nm) are both 92 thermodynamically unstable systems. clouding agents.. 2011). 2011). taste.g. such as gravitational separation.

102 McClements & Rao. In general. 2005b). . but a disadvantage for products where optical clarity is required. recently it has been shown that emulsions with ultrafine droplets. This is an advantage for soft drinks that are required to have a 99 cloudy appearance.g. 2011). Generally. AC C EP TE D 110 120 In this article. to increase their turbidity (“cloudiness”). In addition. but are not too large to undergo gravitational separation (e. McClements. 1982. we will use the term “emulsion” to refer to both nanoemulsions and 121 conventional emulsions because they have similar structures and properties. the size of the 116 droplets within cloud emulsions is designed so that they have dimensions where strong light 117 scattering occurs. 2012. often referred to 101 as “nanoemulsions”. Flavor emulsions contain lipophilic 111 compounds that are primarily present to provide taste and aroma to a beverage product (such as 112 lemon. A major advantage of emulsions and nanoemulsions is that the 103 emulsifier-to-oil ratio required to formulate them is often much less than that required for 104 microemulsions... r = 100-200 118 nm). RI PT 96 Nevertheless. can be prepared that are optically transparent (McClements. Larsson. we focus 106 primarily on the utilization of emulsion systems (conventional emulsions and nanoemulsions) in 107 the preparation of soft drinks but much of the material is also relevant to the formulation of 108 microemulsions. 1992a. Emulsions usually 97 contain larger droplets than microemulsions and therefore they scatter light more strongly and 98 appear more turbid or cloudy. Cloud emulsions are often added to beverages that only contain a relatively low percentage 119 of juice and provide a desirable cloudy appearance that hides sedimentation and ringing. A system 126 that contains oil droplets dispersed within water is called an oil-in-water (O/W) emulsion. or orange oils). lime. such as flavorless vegetable oils. cloud emulsions are used to provide specific 113 optical properties to certain beverage products. 2004. emulsions 125 are classified according to the relative spatial organization of the oil and water phases.e.ACCEPTED MANUSCRIPT 5 and provide sufficient kinetic stability throughout the lifetime of the product. On the other hand. with one of the 123 liquids being dispersed as small spherical droplets in the other (Dickinson. Friberg. Dickinson & 124 Stainsby. & Sjoblom. i. M AN U 109 SC 100 It should be noted that the emulsions used in the beverage industry are typically divided into two groups: flavor emulsions and cloud emulsions. In this article. and they can be formulated from all natural ingredients (such as proteins and 105 polysaccharides) rather than synthetic surfactants (such as Tweens). 114 Cloud emulsions are typically prepared using an oil phase that is highly water-insoluble and that 115 is not prone to chemical degradation. an 122 emulsion consists of at least two immiscible liquids (usually oil and water).

et al.. van der Graaf. forming a protective layer that prevents the droplets from aggregating. & Garti. emulsifiers. 145 Emulsifiers are surface-active molecules that adsorb to the surface of freshly formed droplets 146 during homogenization. including gravitational separation (creaming 139 and sedimentation). Currently. oil-in-water-in-oil 129 (O/W/O). 147 Weighting agents are dense hydrophobic components added to low-density oils to prevent 148 gravitational separation. A more detailed 151 description of different types of stabilizers that can be used in beverage emulsions is given in a 152 later section. water-in-oil-in-water (W/O/W) or oil-in-water-in-water (O/W/W) emulsions 130 (Benichou. Schroen. almost all of the emulsions used in the beverage industry are of the O/W type. e. 2004.. or 143 texture modifiers. ripening inhibitors. it is often difficult to formulate W/O/W emulsions that have sufficient stability for 136 commercial applications.g. 132 although there may be certain advantages to using other emulsion types for certain applications. & Boom. Ripening inhibitors are water-insoluble components added to polar oils 149 to prevent Ostwald ripening. Selecting the most appropriate stabilizer(s) for a particular application is one of the 153 most important factors determining the shelf-life and physicochemical properties of beverage 154 emulsions. 131 2005). Texture modifiers are substances used to increase the viscosity or 150 gel aqueous solutions. 2005b). It is important to clearly distinguish the different physicochemical 144 mechanisms involved in promoting emulsion stability for these different categories of stabilizers. 1992a. McClements. It is possible to prepare more complex emulsion structures.ACCEPTED MANUSCRIPT 6 whereas a system that contains water droplets dispersed in oil is called a water-in-oil (W/O) 128 emulsion.. Aserin. e. SC RI PT 127 Emulsions are thermodynamically unfavorable systems that tend to break down over time 138 though a variety of physicochemical mechanisms. 135 In practice. droplet aggregation (flocculation and coalescence) and droplet growth 140 (Ostwald ripening) (Dickinson. thereby retarding or preventing droplet movement.g. 133 For example. in principle it is possible to trap a hydrophilic bioactive component within the inner 134 water phase of a W/O/W emulsion to protect it from chemical degradation or for taste masking. Friberg. weighting agents. It is possible 141 to form emulsions that are kinetically stable for a reasonable period of time by including 142 substances known as stabilizers. 2004. although this is still an active area of research. 1998. AC C EP TE D M AN U 137 . Garti & Bisperink.

2003). Beverage 165 emulsions may contain a variety of different hydrophobic components. McClements. & Choi. including flavor oils. 2005c). which has often been overlooked in academic research. physical state.ACCEPTED MANUSCRIPT 7 155 3. the more efficient is droplet disruption and the smaller is the particle size 175 produced (Walstra. 183 Henson. the faster the rate of gravitational separation (McClements. oil viscosity influences the efficiency of droplet disruption during high energy 173 homogenization – the closer the ratio of dispersed phase viscosity to continuous phase viscosity 174 (ηD/ ηC) is to unity. 157 stability. and melting point). Droplet composition SC 163 RI PT 156 The composition of the oil phase has a major influence on the formation and stability of beverage emulsions. 2012). molecular partitioning. which leads to changes in their 169 physicochemical properties (such as polarity. nutraceuticals. In this section. Oil density determines the rate of particle creaming or 176 sedimentation within emulsions – the greater the density contrast between the droplets and 177 surrounding fluid. 162 3. density. Oil 178 refractive index determines the efficiency of light scattering by droplets in emulsions – the 179 greater the refractive index contrast between the droplets and surrounding fluid. and functionality of emulsions. rheology. 159 concentration. refractive 170 index. viscosity. and charge (Figure 3). 181 The water-solubility of an oil phase determines the stability of an emulsion to Ostwald ripening 182 due to diffusion of oil molecules through the aqueous phase (Kabalnov. These components vary in their molecular characteristics (such as molecular 168 weight. and 167 ripening inhibitors. Controlling Droplet Characteristics The bulk physicochemical properties of beverage emulsions (such as optical properties. stability. oil-soluble vitamins. First. water-solubility. and functional groups). Decker. triacylglycerol oils. 2005b). Many of these molecular and physicochemical 171 properties have a major influence on the formation.1. the ease of droplet disruption during AC C EP TE D M AN U 164 . we discuss some of the most 160 important droplet characteristics that can be controlled by beverage manufacturers in order to 161 create products with specific desirable functional properties. such as composition. size. 2001. 2002b). weighting agents. Popplewell. For 172 example. and release characteristics) are largely determined by 158 the properties of the droplets they contain (McClements. the stronger the 180 degree of light scattering and the more turbid the appearance (Chanamai & McClements. Oil interfacial tension plays a number of important 184 roles in determining emulsion formation and stability. 1993. 166 essential oils. molecular conformation.

1993). if the physical state of the carrier oil changes. and to understand how specific lipophilic components 201 influence the formation. Horn. 202 3. the rate of droplet coalescence increases as the interfacial tension decreases (Kabalnov 187 & Wennerstrom. Droplet concentration is usually characterized in terms of the dispersed phase volume 206 fraction (φ). Decker. stability. & McClements. Decker. 195 Henson. or if an 197 emulsion is diluted. stability.. 198 water and air (Choi. 1996).ACCEPTED MANUSCRIPT 8 high energy homogenization decreases as the interfacial tension decreases (Walstra. 2009. When the densities of the 210 two phases are equal. M AN U SC 191 It is important for beverage manufacturers to understand the composition of the oil phases 200 used to formulate commercial products. 205 2011). 2010). It is particularly 211 important to convert the droplet concentration to the appropriate units when comparing 212 experimental work with theoretical predictions. which is the volume of emulsion droplets (VD) divided by the total volume of 207 emulsion (VE): φ = VD/VE. which is the mass of emulsion 209 droplets (mD) divided by the total mass of emulsion (mE): φm = mD/mE. which depends 194 on carrier oil type (Choi. 189 Finally. 2005b. Mei. et al. The flavor profile of an emulsion may therefore 196 change if the carrier oil type is altered. the mass fraction is equivalent to the volume fraction. the rate of droplet growth due to Ostwald ripening depends on the interfacial tension at 190 the oil-water interface (Kabalnov.2. sensory attributes. Henson. & McClements. et al. 2002). RI PT 185 For flavor emulsions. 186 Second. 2010b. Beverage emulsions are often prepared in a concentrated form (> 10% oil) because this . appearance. and nutritional quality (McClements. Choi. & McClements. the concentration of droplets in an emulsion influences its texture. Popplewell. Choi. 2010b). it is often more convenient to express the droplet 208 concentration in terms of the dispersed phase mass fraction (φm). since this will change the distribution of the flavor molecules in the oil. It is also important to be aware that the location of 193 the flavor molecules within an emulsion is governed by their oil-water partition. controlling the droplet concentration is important for a number of 214 reasons. Practically.. it is important to control the type and concentration of the flavor 192 molecules initially present in the oil phase. 2009. AC C EP 204 213 In beverage emulsions.. 2001). et al. and properties of final products. Droplet concentration 203 TE D 199 In general. Popplewell. McClements & Rao. Third. the ability of emulsifiers to adhere to droplet surfaces decreases 188 as the bare oil-water interfacial tension decreases (Chanamai.

220 In the concentrate. since emulsion turbidity or cloudiness increases with oil 218 droplet concentration.. but they are highly diluted when they are introduced into the 216 final product (< 0. 2009). EP 236 TE D 226 The particle size distribution (PSD) of an emulsion specifies the concentration of droplets within different size classes.. 2005b). Typically.ACCEPTED MANUSCRIPT 9 facilitates handling and transport.g. The concentration of particles within a particular 241 size class is usually presented as either the volume or number percent. 2007). Droplet size distribution SC The size distribution of the droplets in a beverage emulsion has a strong impact on its M AN U 225 RI PT 215 physical stability (e.1% oil). to gravitational separation. Immediately after the product has been manufactured it is usually 232 important to measure the droplet size distribution to ensure that it has met the specified quality 233 criteria.. coalescence and Ostwald 227 ripening) and its optical properties (e.g..g. Dilution also influences the total amount of flavor molecules present in 219 final products.. et al. lightness and color) (McClements. using light scattering instruments. Beverage 228 manufacturers must therefore specify the optimum droplet size distribution required for their 229 particular product based on the properties required. 224 3. 2005b). but not have the oil content so 223 high that the product is unstable or cannot easily be dispersed into the final product. When presenting or interpreting PSD data on a 239 beverage emulsion it is important to pay particular attention to the manner in which the particle 240 concentration and particle size are presented. They must 230 then develop a formulation and manufacturing process that can reliably produce a beverage with 231 this droplet size distribution. e. whereas the size of the 242 particles in a particular size class is usually presented as either the mid-point particle radius or 243 diameter. From a practical point of view. The same PSD may look very different if it is plotted as volume versus particle size or 244 as number versus particle size. flocculation.g. optical clarity and shelf-life. droplet concentration has a major impact on the rheological properties of the 221 system. It may also be important to measure changes in 234 the droplet size distribution of the product during storage or after an accelerated storage test to 235 predict its long-term stability (McClements. e. as well as their partitioning between the oil and water phases (Choi. and can be conveniently measured using various commercially 238 available instruments (McClements. particle volume versus particle diameter is the most AC C 237 . it may be important to have a high oil loading in the 222 concentrate emulsion so as to reduce transport and storage costs. The amount to which an emulsion concentrate is diluted influences 217 the appearance of a final product.3.


widespread and informative way of presenting particle size data. Commercial beverage


emulsions are always polydisperse systems that can be characterized as being "monomodal",


"bimodal" or "multimodal" depending on whether there are one, two, or more peaks in the


particle size distribution. Typically, beverage manufacturers would like to produce a final


product that has a narrow monomodal distribution, as this usually provides the best long-term






In many practical situations it is important to have knowledge of the full PSD of a beverage
emulsion since this contains information about the size characteristics of all of the particles


present, as well as providing insights into the possible origin and nature of any instability


mechanisms. For example, it may be possible to detect a small population of large particles that


may cause problems with creaming during long-term storage (i.e., ringing). In addition, by


measuring changes in the PSD overtime it is sometimes possible to distinguish between different


instability mechanisms (e.g., coalescence versus Ostwald ripening). Nevertheless, in some


situations it is more convenient to represent the full particle size distribution by a measure of its


central tendency and spread. The mean, median, or modal particle sizes are often used as


measures of the central tendency, whereas the relative standard deviation is often used as a


measure of spread (Walstra, 2003). The mean particle size is the most widely used method of


representing the central tendency of emulsion particle size distributions in the beverage industry.


It is important to realize that a number of different mean particles sizes can be derived from





a full PSD and each mean size can have a different magnitude and physical meaning


(McClements, 2007). The three most commonly used mean particle sizes are the number-


weighted mean diameter (dN or d10 = Σnidi/ Σni), the surface-weighted mean diameter (dS or d32 =


Σnidi3/ Σnidi2) and the volume-weighted mean diameter (dV or d43 = Σnidi4/ Σnidi3). Generally, the


volume-weighted mean diameter is more sensitive to the presence of large particles than the


number-weighted mean diameter, and so it often provides the most rigorous test of the physical


stability of a beverage emulsion, i.e., if d43 is small then the emulsion is more likely to remain


stable. Appreciable differences between the values of d10, d32 and d43 generally indicate that the


particle size distribution is broad or multimodal. One must therefore be very careful when


interpreting or reporting particle size data to identify which mean particle size value (and


corresponding relative standard deviation) is being used. It should also be noted that mean






values should be treated with caution when used to represent highly polydisperse emulsions (e.g.,


aggregated systems), and it is always useful to examine the full particle size distribution.


Commercial beverage manufacturers usually develop a set of standardized particle size
criteria that they use to determine whether a particular batch of product has the desired


physicochemical characteristics, e.g., long-term stability and optical properties. For example, a


manufacturer might specify that that mean droplet diameter (d43) of a particular class of products


should be < 500 nm, and that > 90% of the droplets should be smaller than 800 nm. The precise


criteria used will depend on the product being manufactured (especially whether it should be


clear or opaque).


3.4. Droplet charge


The droplets in most beverage emulsions have an electrical charge because of adsorption of





ionic species to their surfaces, e.g., proteins, ionic polysaccharides, ionic surfactants,


phospholipids, fatty acids, and some small ions (McClements, 2005b). The electrical


characteristics of a droplet surface depend on the type, concentration and organization of the


ionized species present, as well as the ionic composition and physical properties of the


surrounding aqueous phase. The electrical charge on the oil droplets in a beverage may be


important for a number of reasons: it determines the stability of the droplets to aggregation due


to its influence of the magnitude, range and sign of electrostatic interactions; it determines the


interactions of droplets with other charged species in an emulsion e.g., ions (such as calcium or


iron), or polyelectrolytes (such as proteins or polysaccharides); it influences how the droplets


interact with electrically charged surfaces, such as storage vessels, bottles, cups, and the mouth;


it influences the behavior of the droplets in an electrical field, which is important for measuring


their charge using electrophoresis.






The electrical characteristics of a droplet in an emulsion are usually characterized in terms


of its surface charge density (σ), electrical potential (Ψ0), and/or ζ−potential (ζ) (Hunter, 1986).


The surface charge density is the amount of electrical charge per unit surface area, which


depends on the net number of ionized groups per unit interfacial area. The electrical potential is


the amount of energy required to increase the surface charge density from zero to σ. The


electrical potential depends on the surface charge density, but also on the ionic composition of


the surrounding medium due to electrostatic screening effects. At a fixed surface charge density,


the electrical potential decreases with increasing ionic strength due to these effects. The zeta-


potential (ζ) is the electrical potential at the "shear plane", which is defined as the distance away


from the droplet surface below which the counter-ions remain strongly attached to the droplet


when it moves in an electrical field. Practically, the ζ-potential is a better representation of the


electrical characteristics of an oil droplet because it inherently accounts for the adsorption of any


counter ions or ionic species to the droplet surface. In addition, the ζ-potential is more


convenient to measure than the surface charge density or electrical potential (Hunter, 1986).


Typically, the electrical characteristics of the droplets in an emulsion are determined by


measuring the ζ-potential versus pH under appropriate measurement conditions (such as ionic




Droplet aggregation is inhibited in many beverage emulsions by using ionic emulsifiers that





adsorb to the droplet surfaces and prevent them from coming close together because of


electrostatic repulsion (Dickinson, 1992b; Friberg, et al., 2004; McClements, 2005b).


Electrostatic repulsion plays a major role in determining the aggregation stability of fat droplets


coated by charged emulsifiers that only form thin layers that generate short range steric


repulsion, such as globular proteins and ionic surfactants. On the other hand, electrostatic


repulsion is less important in systems where the fat droplets are coated by emulsifiers that form


thick interfacial layers that generate long range steric repulsion, such as polysaccharides (gum


arabic and modified starch). For electrostatically-stabilized emulsions, the magnitude of the ζ-


potential should be greater than about 20 mV to produce systems that are stable during long-term


storage. For sterically-stabilized emulsions, the droplet charge may not be important in terms of


their physical stability, but it may still be important in systems where chemical reactions occur


within the oil droplets that are induced by water-soluble ionic species, such as oxidation of ω-3


fatty acids by transition metals.


3.5. Interfacial properties






The boundary between the oil and water phases in an emulsion consists of a narrow region


(≈ 1 to 50 nm thick) that surrounds each oil droplet, and contains a mixture of oil, water, and


emulsifier molecules, as well as possibly other molecular species, such as mineral ions,


polyelectrolytes, and polar lipids. The interfacial region makes up a significant fraction of the


volume of a droplet when the droplet diameter is less than about 1 µm (McClements & Rao,

thickness. M AN U SC RI PT 335 Beverage manufacturers should therefore be aware of the nature of the interfacial region 352 surrounding the oil droplets in their products. and determines the rate at which molecules leave or 349 enter the droplets (Dickinson. it is often important to have 339 knowledge about the interfacial properties of the droplets in a beverage emulsion. 354 3. and after 344 emulsion formation. These individual interactions vary in their sign (attractive or repulsive). rheology. and hydrophobic interactions (Israelachvili. 2005b). McClements.. which is the energy required to bring two droplets from an infinite distance 360 apart to a surface-to-surface separation of h (Figure 4). and is therefore particularly important in beverage emulsions since they usually contain 336 droplets considerably smaller than this size . e. McClements. 2005b). Colloidal interactions EP 355 TE D 351 The attractive and repulsive colloidal interactions that operate between the oil droplets in beverage emulsions determine their stability to flocculation and coalescence. and to 340 establish the major factors that influence them. interfacial 342 tension. the electrical charge on the droplet interface influences 346 its interaction with other charged molecules. as well as by the events that occur before. with the most important being van der 362 Waals. 2003.. and charge. The 358 colloidal interactions between two oil droplets can be described in terms of an interaction 359 potential (w(h)). the ability of interfacial 350 coatings to prevent droplet flocculation is strongly influenced by their thickness. coalescence and flocculation. Some of the most important properties of the 341 interfacial region are: composition. 363 McClements. The thickness 347 and rheology of the interfacial region influences the stability of emulsions to gravitational 348 separation.ACCEPTED MANUSCRIPT 13 2011). rheology. 2005b). For this reason. The interfacial region can influence many 337 important physicochemical and sensory properties of beverages emulsions. 364 magnitude (weak to strong) and range (short to long). competitive adsorption. 2011. 2004. structural organization. as well as its stability to aggregation. depletion. which in turn 357 influences their creaming stability and rheology (Friberg. As mentioned earlier. including their 338 stability. et al. 2003). For example. electrostatic. concentration and interactions 343 of any surface-active species present. and the fact that they may be able to manipulate its 353 properties to improve product performance.g. during. complexation.6. mouthfeel. Each of the individual interactions usually AC C 356 . steric. The overall interaction potential is made 361 up from contributions from various types of interactions. and flavor. layer-by-layer formation 345 (Dickinson. These properties are determined by the type.

if the beverage emulsion is stabilized by a polysaccharide-based emulsifier. For example. Generally. For example. . as well as in determining the perceived quality attributes of the final 390 product. 381 then steric repulsive interactions will be most important for preventing droplet aggregation. Some of these properties are more important in the concentrated form of the 392 beverage. 387 4. The most important physicochemical attributes of these systems are briefly discussed in 391 this section. then electrostatic repulsive interactions will play an 377 important role in preventing droplet aggregation. if a beverage emulsion 376 is stabilized by a protein-based emulsifier. such as short. which will depend on the molecular characteristics of the 385 polysaccharide molecules. A summary of the major colloidal interactions in beverage emulsions 386 is given in Table 2. In this latter case. such as altering the pH or adding salts (particularly multivalent counter-ions). whereas others are more important in the diluted form.and long-range energy barriers. and 369 primary and secondary minima (Figure 4). 380 On the other hand. transport and storage. This knowledge can then be used to establish the optimum approach for maintaining 375 product stability during production. but remain as individual entities when repulsive interactions dominate 371 (McClements.ACCEPTED MANUSCRIPT 14 has a simple dependence on surface-to-surface separation. the product will be much less sensitive to droplet aggregation when the pH or ionic 383 strength is changed. the interaction potential between two oil 367 droplets coated by a layer of charged polymer molecules would have a number of maximum and 368 minimum values at certain separations. emulsion stability depends on the thickness and 384 hydrophilicity of the interfacial layer. In this situation. Physicochemical Properties M AN U TE D EP AC C 388 SC 373 The physicochemical properties of beverage emulsions play an important role during the 389 manufacturing process. the system will be sensitive to 378 environmental changes that reduce the magnitude and range of the electrostatic repulsion acting 379 between droplets. In 382 this case. droplets tend to aggregate when attractive 370 interactions dominate. but the sum of the interactions can 366 exhibit a more complex dependence. 2005b). 372 RI PT 365 It is particularly important for scientists working in the beverage industry to identify and understand the major colloidal interactions operating between the droplets in their particular 374 product.

whereas others AC C 415 RI PT 395 416 are expected to be cloudy. low L* is dark and high L* is 403 light.1. The opacity of an emulsion can therefore by characterized by the lightness (L*). which can be quantitatively described using tristimulus color coordinates. L* represents the 401 lightness. -b* is the blue direction. the lightness of emulsions increases steeply as the 413 oil droplet concentration increases from about 0 to 5 wt%. Nawar. In this color system. and a* and b* are color coordinates: where +a* is the red direction. a dark brown cola. SC M AN U TE D EP As mentioned earlier. e. 2002b. Decker. The optical properties of emulsions are mainly determined by the relative refractive 407 index. Danviriyakul. McClements. 409 McClements. 2005b).05 cm-1 (at 600 nm) can be considered to be a rough cut-off point between . As a rule of thumb. From a scientific viewpoint. a cloudy orange juice. 419 For clear products. so that the chroma decreases (fades) when the lightness 406 increases. while the 404 color intensity can be characterized by the chroma: C = (a*2 + b*2)1/2. Optimizing the initial particle size distribution of a beverage 417 emulsion. This has important implications for the development of beverage products that 412 should be either clear or opaque. In general. & Sanguansri. concentration. 400 such as the L*a*b* system (McClements. 396 such as a bottle or cup). Each type of beverage product is expected to have a particular 397 appearance depending on its nature. the majority of droplets should be less than about 50 nm in diameter so that 420 the light scattering is very weak (Wooster. a 423 turbidity of 0. +b* is the yellow direction. & Chinachoti. 2008a).ACCEPTED MANUSCRIPT 15 393 394 4. as well as inhibiting any changes in the particle size during storage. The color intensity is 405 usually inversely related to the lightness. The lightness of an emulsion tends to increase with increasing refractive 410 index contrast and increasing droplet concentration. The scattering 421 efficiency of the individual oil droplets determines the maximum amount of oil phase that can be 422 incorporated into a clear beverage before it becomes noticeably cloudy. 2002. Optical properties The first cue that a consumer uses to judge the quality or desirability of a finished beverage product is its visual appearance (provided it is packaged or poured into a transparent container. emulsion appearance is categorized in terms of 399 their opacity and color.. Golding. some beverages are expected to have optical clarity. and has a maximum value at a particular 411 droplet size.g. 2005b). and size distribution of the droplets they contain (Chanamai & 408 McClements. or a clear 398 green lime juice. is therefore a 418 particularly important part of designing a commercial product with the desired optical properties. -a* is the green 402 direction. but then increases more gradually at 414 higher droplet concentrations (Figure 5).

Most beverage emulsions are initially manufactured in a 432 concentrated form. For cloudy products. the rheology of the beverage 435 concentrate is important since it influences the ease of mixing. Lozano.1%. η is the viscosity of the overall system. which is diluted appreciably during the production of the final beverage 433 product.2. The droplet concentration in the beverage concentrate typically ranges from 3 to 30%. it still provides a good approximation of the 452 rheological properties of dilute beverage emulsions because the flow of the liquid within the oil 453 phase is inhibited by the emulsifier coating. flow through a pipe. The above equation shows that the viscosity of a .5φ ) (1) AC C 445 EP 441 Here. η0 is the viscosity of the continuous phase. Industrially. The droplet concentration in the final beverage 439 concentration is usually so low that the rheology is dominated by the properties of the aqueous 440 continuous phase (see discussion below). TE D M AN U SC 431 The rheology of dilute colloidal dispersions is normally characterized by the shear viscosity 442 (Genovese. & Rao. without 437 the product becoming too viscous or gel-like to handle easily. 2002). 2007. McClements. In this case. 450 Einstein’s equation was derived assuming that the colloidal particles were rigid isolated spheres 451 surrounded by a Newtonian fluid. A manufacturer typically wants to have as high an oil loading as possible. 434 while that in the final product is typically < 0. 2005b). the shear viscosity can be described by Einstein’s equation: 444 446 447 η = η 0 (1 + 2. Rheology 430 RI PT 424 The rheological properties of beverage emulsions are also an important factor determining their manufacture and utilization. the scattering efficiency of the individual oil droplets will 427 determine the minimum amount of a clouding emulsion required to reach a particular turbidity in 428 the final product.ACCEPTED MANUSCRIPT 16 transparent and cloudy products. and 436 packaging. This requires careful control of 438 the total droplet concentration in the system. This equation under-predicts the viscosity of colloidal 449 dispersions with higher droplet concentrations due to the effects of droplet-droplet interactions. the majority of droplets should be 425 between about 200 and 400 nm in diameter so that the light scattering is very strong 426 (McClements. 429 4. Nevertheless.05). and 448 φ is the disperse phase volume fraction. When the droplet concentration is less 443 than about 5% (φ < 0.

2005b). 2003). McClements. Molecular distribution and release characteristics TE D EP AC C 475 M AN U 463 A beverage emulsion may contain a number of constituents that partition into different 476 phases within the product. The 480 chemical stability of these constituents is often dependent on their molecular environment.g. oil. & Quemada. e. et al. 469 In flocculated systems the critical concentration where the system becomes highly viscous or 470 solid-like may be much lower than in a non-flocculated system. 2007.. 2005. 2005b. Quemada & Berli. φ is the disperse phase volume fraction. 473 Walstra. 474 4. but that the most important factor 455 affecting the overall rheology is the viscosity of the continuous phase. 460 2005b.. interfacial. 458 RI PT 454 The viscosity of concentrated emulsions can be described by a semi-empirical equation that 459 takes into account droplet-droplet interactions (Berli. For example. It is therefore important for 471 beverage manufactures to consider the influence of droplet concentration and interactions on the 472 rheological properties of emulsion concentrates (Genovese. Quemada & Berli. 477 The physical location of some of these constituents may have a major impact on the quality 478 attributes of the final product. gradually initially and then steeply as the droplets become more 466 closely packed (Figure 5). Around and above the droplet concentration where close packing 467 occurs. 2002): −2 461  φ η = η 0 1 −  φc 462 Here. et al. citral). Deiber. McClements. Thus the most effective 456 means of controlling the viscosity of a dilute beverage emulsion is to change the viscosity of the 457 continuous phase. by adding sugars or polymer thickening agents. 2005b. 2002)..3. aqueous. For 481 example. the emulsion becomes highly viscosity and may exhibit solid-like characteristics.g.63) is a critical disperse phase (2) SC    volume fraction above which the droplets are so closely packed together that they cannot easily 464 flow past each other. or gas phases (McClements. the rate of acid-catalyzed degradation of citral has been shown to occur considerably 482 faster when it is located within an aqueous phase than when it is present within an oil phase . e..g. McClements. and φc (≈ 0. many flavor oils contain constituents that are 479 chemically unstable and therefore prone to degradation during storage (e. such as 468 visco-elasticity and plasticity (Berli..ACCEPTED MANUSCRIPT 17 dilute emulsion increases linearly with droplet concentration. 2005. This equation shows that the viscosity of an emulsion increases with 465 increasing droplet concentration.

Choi. variations in solution 508 properties (e. pasteurization. pH and mineral composition of water). Beverage Emulsion Shelf-Life TE D M AN U SC 491 One of the most important factors determining the commercial viability of beverage 502 emulsions is their ability to resist changes in their physical and chemical properties after their 503 production.g. flow through a pipe.g. 2005b). transport.g. Beverage emulsions experience a range of environmental stresses during their 504 manufacture. exposure to light 507 (e. 2005b). changes in solubility. natural or artificial visible or ultraviolet waves). e. fortification with a bioactive lipid such as ω-3 oils. oxidation. This phenomenon is 489 important to take into account when reformulating a beverage product so that it contains a 490 different fat concentration. centrifugation. Increasing the oil 487 content of an emulsion decreases the concentration of hydrophobic (KOW > 1) volatiles in the 488 headspace and therefore reduces the perceived flavor profile (Figure 6). temperature 506 variations (e. et al.. exposure to oxygen. Exposure to these environmental 509 stresses may promote emulsion instability through a variety of physicochemical mechanisms: 510 loss of ingredient functionality (e.ACCEPTED MANUSCRIPT 18 (Choi. polymerization. oil-interface) and its mass transport kinetics through 493 the system (McClements..1 s for KOW < 1000). or stabilization 511 capacity). and therefore droplet dimensions 497 tend to have little impact on the flavor release profile (McClements. 2009... vibrations. it 498 may be possible to encapsulate oil droplets within hydrogel matrices to slow down the release of 499 flavor molecules within the mouth.. 500 5. freezing. chilling. or AC C EP 501 .. This would suggest that it is better to keep citral under 484 neutral conditions or within the emulsion concentrate as long as possible before the final dilution 485 into the acid phase is carried out. When a beverage emulsion is placed in the mouth there is a 494 redistribution of flavor molecules.. acceleration of chemical degradation reactions (e. The rate at which flavor molecules leave the droplets in beverage 496 emulsions is usually extremely quick (< 0.g. et al. with some of the aroma compounds leaving the product and 495 entering the nasal cavity. 2010b). RI PT 483 The location of a constituent within a beverage emulsion is governed by its equilibrium 492 partition coefficients (e.g. and pouring).g. storage. Nevertheless.g. and utilization that may reduce their shelf lives: mechanical 505 forces (e.. The perceived flavor profile of beverage emulsions depends on 486 the distribution of volatile molecules between the liquid and gas phases. warming... oil-water. stirring. surface activity. oil-air. and sterilization).g.

changes in the chemical structure of active components can lead to 523 changes in physical stability. 528 Creaming is the upward movement of droplets when they have a lower density than the aqueous 529 phase. and it may take the form of either creaming or sedimentation 527 depending on the relative densities of the oil droplets and the surrounding aqueous phase. acceleration of physical instability mechanisms. 519 flocculation. All of these instability mechanisms lead to a change in the structural 521 organization of the various components within the system. 1992a.g.. due to flocculation. which is the 537 accumulation of a visible ring of oil droplets on the top of a product. In this section.ACCEPTED MANUSCRIPT 19 hydrolysis). including gravitational separation. However. et al. or because some droplet growth occurred during storage. 540 coalescence. Friberg. 520 McClements. or Ostwald ripening (see later sections). (e. 2005b).1. which may have occurred because a population of droplets in the initial emulsion was 539 too large. coalescence or 513 Ostwald ripening). e.. and some suggestions for preventing them from occurring are 515 provided. and vice versa. a brief overview of some of the major instability mechanisms 514 in beverage emulsions is given. This effect is due to droplet 538 creaming. flocculation. 516 5. Physical Stability 517 RI PT 512 Emulsions are thermodynamically unfavorable systems that tend to break down over time due to a variety of physicochemical mechanisms (Figure 2). 2011). the velocity that 541 an oil droplet moves upwards in a dilute emulsion due to gravity is given by Stokes’ law: . Nevertheless. 2004. A beverage emulsion is also prone to 534 sedimentation if it contains very small oil droplets covered by relatively thick and dense 535 interfacial layers (see below) (McClements.. Gravitational Separation M AN U 525 SC 518 Gravitational separation is one of the most common forms of physical instability in commercial beverage emulsions. rather than in the type of molecules 522 present.1.1. AC C EP TE D 526 536 One of the most common problems reported in beverage emulsions is “ringing”. coalescence and Ostwald ripening (Dickinson. whereas sedimentation is the downwards movement of droplets when they have a higher 530 density than the aqueous phase. The oil phases used in beverage emulsions consist primarily of 531 triacylglycerol and/or flavor oils. To a first approximation. which have lower densities than water and so creaming is more 532 prevalent (Table 3).g. 524 5. if a beverage emulsion contained an excess of weighting agent 533 within the oil phase then it may be prone to sedimentation.

ACCEPTED MANUSCRIPT 20 2 2 grparticle ( ρ particle − ρ 0 ) 542 v=− 543 where. In practice. or the aqueous phase 547 viscosity increases. 556 Consequently. 2011). RI PT SC M AN U Gravitational forces tend to dominate droplet movement in emulsions TE D 559 (3) 9η 0 The above calculations assume that the particles in beverage emulsions are homogeneous spheres consisting entirely of oil phase. so that an (4) 567 increase in the volume fraction of the shell layer will tend to increase the overall particle density. the density contrast decreases. η0 is the aqueous phase viscosity. Hence. Brownian motion favors the random distribution of the 552 droplets throughout the entire volume of the emulsion. the 562 overall particle radius is given by rparticle = rcore + δ. then the droplets would accumulate at either the top or the bottom 550 of an emulsion. ρ0 is the aqueous phase density. and g is the 545 acceleration due to gravity. rather than their accumulation at either 553 the top or bottom. emulsions become more stable to creaming or sedimentation as the particle size 557 decreases because the creaming velocity decreases (v ∝ r2) and because Brownian motion effects 558 increase. Gravitational forces cause droplets to move either upwards or downwards 548 depending on their density relative to the surrounding aqueous phase. v is the creaming velocity. consisting of an oil core and an interfacial shell. and the overall particle density (ρparticle) 563 depends on the densities of the core (ρC) and shell (ρS) materials and the volume fraction of the 564 shell (Φ S): AC C EP 560 565 ρ particle = Φ S ρ S + (1 − Φ S ) ρ C 566 The shell layer usually has a higher density than the oil or aqueous phases. if only 549 gravitational forces operated. very small particles may actually sediment rather than cream if they contain . This equation shows that the rate of droplet creaming should 546 decrease as the droplet size decreases. 568 This has important implications for preventing gravitational separation in beverage emulsions 569 with small droplets sizes since it reduces the density contrast between the particles and aqueous 570 phase. droplets may also move because of Brownian motion associated 551 with the thermal energy of the system. In addition. ρparticle is the particle 544 density. In this case. rparticle is the particle radius. whereas Brownian motion forces tend to 555 dominate droplet movement in emulsions containing smaller droplets (McClements. the particles in beverage emulsions actually 561 have a core-shell structure. 554 containing relatively large droplets (r > 100 nm). In practice.

This approach may not always be viable since it will also influence 588 the texture and mouthfeel of the final product. such as their 596 appearance (cloudiness or homogeneity). As already mentioned.. since the creaming velocity is proportional to the droplet size 584 squared (Stoke’s Law). e. depending on the 578 amount of sugars and other solutes present (Table 3). Droplet Aggregation The aggregation state of the droplets in a beverage emulsion is important because it AC C 593 EP 590 594 influences the stability of the product to gravitational separation. it should be possible to produce density 572 matched particles in beverage emulsions by controlling the oil core size and the thickness of the 573 adsorbed emulsifier layer. If the droplets are sufficiently small. M AN U TE D 589 SC 575 Another approach some beverage manufacturers have used to mask the undesirable effects of creaming (“ringing”) on the appearance of a product is to design the packaging so as to 591 obscure the effect. then Brownian motion effects will 585 dominate and the system will remain stable to creaming or sedimentation. and therefore oil droplets will tend to move upwards. First. with appropriate placement of the labels or cap. 592 5..g. by adding 587 thickening or gelling agents. gravitational 586 separation can be inhibited by increasing the viscosity of the aqueous phase. The 577 density of the aqueous phase typically varies from about 1000 to 1050 kg m-3. Third. The tendency for droplet aggregation to occur in a 597 beverage emulsion depends on the balance of attractive and repulsive forces operating between 598 the droplets (see earlier). oil core characteristics (such as radius). Thus.ACCEPTED MANUSCRIPT 21 571 sufficiently thick and dense emulsifier layers. The density of most oil phases is less than 579 this value. gravitational separation can be 576 prevented by matching the density of the dispersed (oil) and continuous (aqueous) phases.g. the 580 density of the core-shell particles within a beverage emulsion can be matched to the surrounding 581 aqueous phase by adding a weighting agent to the oil phase. Second.2. Changes in particle size during 595 storage may also influence other important quality attributes of beverage products.1.g. water and interfacial 600 phases (e.. . The nature of the colloidal interactions operating in a particular 599 beverage emulsion depends on the physicochemical properties of the oil. or by controlling the thickness and 582 density of the emulsifier layer. e. dielectric constant and refractive index). gravitational separation can be inhibited by reducing the 583 size of the droplets in the emulsion. The above discussion has highlighted a number of approaches that can be used to inhibit or RI PT 574 prevent gravitational separation in beverage emulsions.

This is usually achieved by using an emulsifier that generates repulsive 617 interactions between the droplets. AC C EP TE D M AN U 610 628 The droplets in emulsions are in continual motion because of the effects of thermal energy. and the properties of the intervening fluid (such as pH. whereas the magnitude and range of the electrostatic repulsion depend on the 614 droplet charge (ζ-potential) and the ionic composition of the aqueous phase. or applied mechanical forces. The van der Waals attraction operates between all 611 kinds of droplets and would always cause aggregation if there were no opposing repulsive forces.ACCEPTED MANUSCRIPT 22 interfacial shell characteristics (such as thickness. ionic strength. To design a product 615 that is stable to droplet aggregation one must assure that the repulsive interactions dominate the 616 attractive interactions. 612 The magnitude and range of the steric repulsion depend on the thickness and chemistry of the 613 interfacial layer. and 622 thereby stabilize the system against aggregation. 627 e. 605 electrostatic (wE). emulsifiers that can only stabilize emulsions due to 625 electrostatic interactions may be prone to instability when the pH or ionic strength is changed. such as casein and whey proteins. rheology and 602 hydrophobicity).g.. charge. 631 depending on the relative magnitude of the attractive and repulsive interactions between them. The emulsifiers used in the beverage industry typically 618 stabilize the droplets against aggregation by generating steric and/or electrostatic repulsive 619 interactions. osmotic 603 pressure. Emulsifiers that form relatively thick open interfaces (such as polysaccharides and 620 non-ionic surfactants with large hydrophilic head-groups) can generate a steric repulsion that is 621 sufficient strong and long range to overcome the attractive van der Waals interactions. and steric (wS) interactions (McClements. emulsion droplets may either move apart or remain aggregated. whereas the steric and electrostatic SC 609 RI PT 601 interactions are usually repulsive (Table 2). To a first approximation the overall colloidal interactions between a 604 pair of droplets in a beverage emulsion can be described by the sum of the van der Waals (wVDV). 2005b): 606 607 w(h) = wVDV(h) + wE(h) + wS(h) (5) 608 The van der Waals interactions are attractive. However. After a collision. Emulsifiers that form highly charged interfaces 623 (such as proteins and ionic surfactants) can generate a strong electrostatic repulsion between 624 droplets that prevent aggregation. 626 Some emulsifiers use a combination of electrostatic and steric repulsion to stabilize the system. . and as they move about they frequently collide with their 630 neighbors. packing. and temperature). 629 gravity.

Flocculation may occur in beverage emulsions through a variety of different processes 643 that either increase the attractive forces or decrease the repulsive forces operating between the 644 droplets. 1997a. 660 2011). (ii) counter-ions bind to the surface of 651 the droplets and reduce their charge (“charge neutralization”). SC M AN U 647 RI PT 632 Reduced electrostatic repulsion: Electrostatically stabilized emulsions may flocculate when the electrostatic repulsion between the droplets is reduced.g. The mechanism that is important in a particular emulsion depends largely on the nature 645 of the emulsifier used and the solution conditions (e. 641 This may be undesirable since it would influence the transport. 655 Coupland. EP AC C 656 TE D 648 Increased depletion attraction: The presence of non-adsorbing colloidal entities in the 657 continuous phase of an emulsion. and may even lead to the formation of a gel. ion type and concentration. pH. (iii) the ionic strength of the 652 aqueous phase is increased to screen the electrostatic interactions (“electrostatic screening”).1. handling and dispersibility of the 642 product. and 646 functional ingredients). A number of physicochemical 649 changes may cause this reduction in electrostatic repulsion (Israelachvili.2. until 661 eventually it becomes large enough to overcome the repulsive interactions between the droplets and .. such as biopolymers or surfactant micelles. generates an 658 increase in the attractive force between the droplets due to an osmotic effect associated with the 659 exclusion of the colloidal entities from a narrow region surrounding each droplet (Israelachvili. McClements. 635 636 5.ACCEPTED MANUSCRIPT 23 Droplets aggregate when there is a primary or secondary minimum in the interaction potential 633 that is sufficiently deep and accessible to the droplets (Figure 4). Droplet flocculation 638 is usually detrimental to beverage emulsion quality because it accelerates the rate of gravitational 639 separation thereby reducing their shelf-life. 2011): (i) the pH is 650 altered so that the net charge on the droplets is reduced. This attractive force increases as the concentration of colloidal entities increases. & McClements. Flocculation Droplet flocculation is the process whereby two or more droplets come together to form an 637 aggregate in which the droplets retain their individual integrity (Figure 2). The two major types of 634 aggregation in beverage emulsions are flocculation and coalescence.1. Flocculation can also cause an appreciable increase 640 in the viscosity of beverage emulsion concentrates. 653 Protein-coated oil droplets are particularly sensitive to flocculation due to reduction in the 654 electrostatic repulsion between them when the pH or ionic composition is altered (Demetriades. 2004).

& Robins. Guzey & McClements. Exposure of these non-polar amino acids increases the hydrophobic 678 character of the droplet surface and therefore leads to flocculation because of the increased 679 hydrophobic attraction between the droplets. The presence of relatively high concentrations of non-adsorbed biopolymer 664 emulsifiers (gum arabic and modified starch) have been shown to induce depletion flocculation in 665 model beverage emulsions (Chanamai & McClements. 2004. whey protein stabilized emulsions (pH 7) are stable 674 to flocculation because of the large electrostatic repulsion between the droplets. 668 2009. & 673 McClements. 691 692 AC C EP 680 The development of a suitable strategy to prevent droplet flocculation in a particular beverage emulsion therefore depends on identification of the physicochemical origin of . & Wedlock. Gu. Hibberd. Decker. Biopolymers may adsorb either directly to the 682 bare oil surfaces of the droplets or to the adsorbed emulsifier molecules that form the interfacial 683 layer. 1990. carrageenan or xanthan) 689 might adsorb to the surface of two positively charged droplets causing them to flocculate 690 (Dickinson. 2003). but when they 675 are heated above 70 oC they become unstable.ACCEPTED MANUSCRIPT 24 causes them to flocculate. Cho & McClements. 667 pectin. Depletion flocculation may also be 666 promoted by other kinds of biopolymers that might be used in beverages. 686 For example. xanthan gum. 1997b). such as maltodextrin. 2006). a positively charged biopolymer (such as chitosan) might adsorb to the surface of 687 two negatively charged emulsion droplets causing them to flocculate (Ogawa. 2003) or a negatively charged biopolymer (such as pectin. 2003. This type of droplet aggregation is usually referred to as depletion 663 flocculation. To be able to bind to the droplets there must be a sufficiently strong attractive interaction 684 between segments of the biopolymer and the droplet surface. 1988). Howe. The globular proteins adsorbed to the surface of 676 the droplets unfold above this temperature and expose non-polar amino acids that were originally 677 located in their interior. Coupland. At room temperature. The most common types of 685 interaction that operate in food emulsions are hydrophobic and electrostatic (Dickinson. Dickinson. & 688 McClements. & McClements. 669 RI PT 662 Increased hydrophobic interactions: This type of interaction is important in emulsions that contain droplets that have some non-polar regions exposed to the aqueous phase. TE D M AN U SC 670 Formation of biopolymer bridges: Many types of biopolymer promote flocculation by 681 forming bridges between two or more droplets. Decker. Gunning. A good 671 example of this type of interaction is the effect of thermal processing on the flocculation stability 672 of oil-in-water emulsions stabilized by globular proteins (Demetriades. 2001). and carrageenan (Cao.

Kabalnov & Shchukin. The stability of emulsions to coalescence can be improved by preventing the droplets 709 from coming into close proximity for extended periods. The driving force for this effect is the fact that .. In beverage emulsions.g.2. Coalescence causes emulsion droplets to cream or sediment 699 more rapidly because of the increase in their particle size.1. e.e. 710 preventing the formation of a creamed layer.2. e. 1992). Coalescence Coalescence is the process whereby two or more liquid droplets merge together to form a 698 single larger droplet (Figure 2). Mechanistically. Ostwald Ripening EP AC C 715 TE D 704 This susceptibility of a beverage emulsion to Ostwald ripening (OR) is mainly determined 716 by the solubility of the oil phase in the aqueous phase: the higher the solubility. but oil phases with relatively high water- 719 solubilities (such as flavor or essential oils) may be highly unstable. the more 717 unstable the emulsion. In general. 2005b). the susceptibility of oil droplets to coalescence 706 is determined by the nature of the forces that act between the droplets (i. Alternatively.3. hydrodynamic and mechanical forces) and the resistance of the interfacial layer to 708 rupture. and that there are no additives that can promote 695 bridging. which is referred to as 701 oiling off. 696 697 5. by preventing droplet flocculation. flocculation can be prevented by ensuring that the 694 repulsive forces dominate the attractive forces.. since this instability mechanism involves 705 two or more droplets fusing together. Oil phases with very low water-solubilities (such as the vegetable oils 718 used in clouding emulsions) do not exhibit OR. coalescence 700 eventually leads to the formation of a layer of oil on top of the material.ACCEPTED MANUSCRIPT 25 flocculation in that system. 714 5.1. 707 colloidal. 2001. by selecting an appropriate 713 emulsifier or other additives that alter surface properties. SC The susceptibility of a beverage emulsion to droplet coalescence is highly dependent on the M AN U 703 RI PT 693 nature of the emulsifier used to stabilize the system. one can control the properties of the interfacial layer 712 surrounding the oil droplets to make it more resistant to rupture. gravitational. In general. OR is the 720 process whereby the size of the oil droplets in an oil-in-water emulsion increases over time due 721 to diffusion of oil molecules from small to large droplets through the intervening aqueous phase 722 (Kabalnov.g. This process is one of the main reasons for the shiny oily layers often seen on top of 702 unstable beverage emulsions. or having too high droplet concentrations 711 (McClements.

. or fish oils). Herrmann. AC C EP TE D 739 750 Consider an oil-in-water emulsion that contains droplets comprised of two different lipid 751 components: a water-insoluble component and a water-soluble component. 745 2012. d(t) is the number-weighted mean droplet diameter at time t. McClements. corn. 1999).g.. OR can be retarded in these systems by adding 746 a substance known as a ripening inhibitor. a long chain triacylglycerol (such 748 as corn oil). Vm is the molar volume of the oil.ACCEPTED MANUSCRIPT 26 the water-solubility of an oil contained within a spherical droplet increases as the radius of the 724 droplet decreases. Xiao. 2008b). R is the gas constant. This type of molecule can inhibit OR by generating an entropy of mixing effect that 749 counter-balances the curvature effects. The presence of this concentration gradient means that 727 solubilized oil molecules tend to move from the immediate vicinity of smaller droplets to that of 728 larger droplets. A ripening inhibitor is a non-polar molecule that is 747 soluble in the oil phase but insoluble in the water phase. such as 744 flavor oils and essential oils (Li. & Sanguansri. S∞ is the water- 736 solubility of the oil phase in the aqueous phase. Wooster. α =2γVm/RT. For this reason 741 OR is not usually a problem for emulsions prepared using oils with a very low water-solubility. 2009. The most important factor determining the stability of a beverage emulsion to OR is the 740 water-solubility of the oil phase (S∞) (Weiss. 1992.. 1992): RI PT 723 732 d (t ) 3 − d ( 0 ) 3 = ω t = 32 9 αS ∞ Dt (6) M AN U 733 734 SC 731 Here. Consequently. soy. d0 is the initial number- 735 weighted mean droplet diameter. et al. 742 such as long chain triglycerides (e. On the other hand. and T is the absolute temperature. 2005b). OR 743 may occur rapidly for emulsions prepared using oils with an appreciable water-solubility. Le Maux. & McClements. This leads to an increase in mean droplet size over time. γ is the oil-water 738 interfacial tension. ω is the Ostwald ripening rate. & McClements. sunflower. e. McClements. Golding.g. which can be described 729 by the following equation once steady state conditions have been achieved (Kabalnov & 730 Shchukin. which means that there is a higher concentration of solubilized oil molecules 725 in the aqueous phase surrounding a small droplet than surrounding a larger one (Kabalnov & 726 Shchukin. The water-soluble 752 molecules will diffuse from the small to the large droplets due to OR. D is the translational diffusion coefficient of the 737 oil molecules through the aqueous phase. there will 753 be a greater concentration of water-insoluble molecules in the smaller droplets than in the larger .

and 768 therefore it can retard OR if it is incorporated into the oil phase prior to homogenization. 1982. & 782 Mizutani. the formation of terpene alcohols. OR may also be retarded by adding certain kinds of weighting agents 771 (such as ester gums) since these substances also have a very low water solubility and therefore 772 act as ripening inhibitors (Lim. 1983b). et al. Nishimura. 773 5. Chemical Stability SC M AN U TE D EP 774 RI PT 754 A number of lipophilic compounds that may be present in beverage emulsions can undergo chemical degradation during storage. 1977. The change in droplet size distribution with 759 time then depends on the concentration and solubility of the two components within the oil 760 droplets. which leads to a loss of color. This approach has previously been used to improve the stability of food-grade 761 nanoemulsions. et al. Kimura. hydrolytic 780 reactions. et al. An example of this effect is 763 shown in Figure 7 which shows that droplet growth in orange oil-in-water emulsions during 764 storage can be inhibited by adding a sufficiently high concentration of corn oil (the ripening 765 inhibitor) (McClements. Wooster.. there is a thermodynamic driving force that 758 operates in the opposite direction to the OR effect. essential oils.ACCEPTED MANUSCRIPT 27 droplets after OR occurs. 2011). A 776 few representative examples of chemical degradation of lipophilic components in oil-in-water 777 emulsions are given below. et al. On the other hand. and therefore is highly prone to OR. 778 AC C 775 Citrus Degradation. which leads to an appreciable increase in mean 767 droplet size during storage. flavor and/or nutrients. 2012)... Several mechanisms lead to the chemical decomposition of citrus flavor 779 components (such as citral. 1983a. and citronellal). rather than to 757 be located in particular droplets. such as those containing short chain triglycerides. et al. 2012. These 769 results show that incorporating ≥ 10% corn oil into the oil phase was sufficient to inhibit OR in 770 these systems (Figure 7). Acid-catalyzed decomposition and oxidation reactions change the 783 desirable flavor profile of citrus oils by reducing the concentration of desirable flavor . and flavor oils 762 (Li. & Radford. Differences in the composition of emulsion droplets are 755 thermodynamically unfavorable because of the entropy associated with mixing: it is more 756 favorable to have the two lipids distributed evenly throughout all of the droplets. d-limonene. Iwata. corn oil has a very low solubility in water. & Nishimura. Orange oil (4-fold) has a relatively high solubility in 766 water. Kimura. 781 Powell.. 2009.. Iwata. McClements.2. and the cyclization of terpene aldehydes (Clark. including oxidation.. 2008b). Consequently.

.ACCEPTED MANUSCRIPT 28 784 components and increasing the concentration of undesirable flavor components (Tan. Ho. The chemical stability of citral has been shown to be much 793 higher when it is located within an oil phase than in an aqueous phase (Choi. 2001. 2010b). et al. 2007. the chemical degradation of citral in beverage emulsions can be improved by 795 ensuring that the citral molecules are located primarily in an oil phase rather than in the aqueous 796 phase. The degradation rate of citral in aqueous solutions has been shown to 790 increase with decreasing pH (Choi. Henson. 2004). Indeed. Indeed. It was proposed that citral stability may be improved by encapsulating it within solid 800 lipid particles rather than within liquid oil droplets. et al. Decker. 794 Consequently. Masuda. Ho. and so it may be possible to improve the 806 stability of the citral molecules within them by engineering the properties of the interfacial layer 807 (Decker & McClements.. 814 Cercaci. 2009). 2011). 2004. 2008. although these strategies may not be practical for most commercial 799 products. Tian. studies have shown that citral stability can be improved by increasing the oil 797 droplet concentration (Choi... & Huang. Addition of various kinds of natural 803 antioxidants to flavor oil emulsions has also been shown to improve the stability of citral to 804 chemical degradation (Yang. et al. Given Jr. The oil droplets in beverage emulsions 805 are surrounded by a coating of emulsifier molecules. which was attributed to the expulsion of the citral molecules into the aqueous 802 phase after droplet crystallization (Mei. Coating flavor oil droplets with a cationic biopolymer layers 813 has also been shown to improve the stability of citral to chemical degradation (Djordjevic. & Decker. There has been a great deal of research on establishing the major factors that influence the RI PT 787 chemical degradation of citral because this is one of the most important flavor compounds found 789 in commercial beverages.. 785 Ueno. Most commercial beverages have 791 acidic aqueous phases and are therefore highly susceptible to flavor loss during storage due to 792 this acid-catalyzed mechanism. however the opposite was found to be true 801 experimentally. Alamed. 2009) or by adding surfactant micelles to the aqueous phase 798 (Choi. Tian. & Ho. McClements. 811 2010a). et al. 2010). & Huang.. 2009). Popplewell. A high local concentration of protons is believed to accelerate the citral degradation 812 mechanism at the droplet surfaces. studies have shown that citral 808 degradation was faster in flavor oil droplets coated by an anionic surfactant than those coated by 809 a non-ionic or cationic surfactant. The beverage industry would therefore like to identify effective 786 strategies for preventing these undesirable chemical degradation reactions. 2009) (Figure 8). et al. which was attributed to differences in the accumulation of 810 catalytic protons near the droplet surfaces (Choi. 2012) AC C EP TE D M AN U SC 788 . & McClements. Yang.

& O'Brien. Lipid oxidation 820 affects the quality of emulsion-based products. or light. including highly acidic environments 840 (Konovalov & Kispert. 832 Carotenoid degradation. storage conditions. Based on this knowledge a variety of 828 strategies have been developed to inhibit or prevent lipid oxidation in emulsified products: 829 addition of oil-soluble and water-soluble antioxidants. 1996). 2001). fish and algal oils) since these lipids have 817 been claimed to have health benefits and are currently under-consumed by the general 818 population. 1964). & Decker. McClements. 1997). odor. 2003. oxygen. 1996. Woodall. & Britton. 1996. singlet 841 oxygen (Krinsky. 2008). chelation of pro-oxidant transition metals. controlling environmental conditions. The oxidation of polyunsaturated lipids is a 822 highly complex series of chemical reactions that is initiated when a lipid interacts with an 823 oxygen reactive species. O'Connell. Jackson. there are many technical difficulties associated will incorporating 819 these lipids into beverage products due to their high susceptibility to oxidation. & Decker. et al. 830 engineering the interface to prevent pro-oxidants from coming into close proximity to lipid 831 substrates. O'Sullivan. & German. Nevertheless. heat (Mader. and proceeds through molecular cleavage and oxygen addition reactions 824 to the formation of a wide variety of volatile compounds (McClements & Decker. influencing their flavor. light (Mortensen & Skibsted. Williams. Satué-Gracia. Carotenoids are natural compounds found in many fruits and 833 vegetables that are may be used in foods an colorants or nutraceuticals because of their potential 834 health benefits (Mayne. Weesie. 2000. Lee. apocarotenals and apocarotenones (Gao & Kispert. 2003. and nutritive value 821 (Frankel. 844 including epoxides. Aherne. Once 843 carotenoid degradation has been initiated a number of secondary reaction products may form.. such as exposure to heat. transition metals (Gao & Kispert.ACCEPTED MANUSCRIPT 29 815 Polyunsaturated Lipid Degradation. 1999). and the structural organization of the system. 2011). A number of factors have previously 839 been shown to promote the oxidation of carotenoids. 2009). 1998). There has been great interest in the beverage industry in fortifying products with ω-3 lipids (such as flax. Weiss. endoperoxides. and free 842 radicals (Liebler & McClure. One of 835 the major factors currently limiting the incorporation of carotenoids into many food and 836 beverage products is their high susceptibility to chemical degradation. Meyer. carotenoids 837 have a conjugated polyunsaturated hydrocarbon chain that makes them highly prone to 838 autoxidation (Boon. 2002). the presence of pro-oxidants and 827 antioxidants. 825 McClements. The rate at which oxidation takes place is dependent on several 826 factors: the molecular structure of the lipids. AC C EP TE D M AN U SC RI PT 816 . Ryan. Waraho. In particular.

Coenzyme Q10. which depends on the rate of the various physical and chemical 858 instability mechanisms occurring. The . we briefly describe the major characteristics 869 of the concentrate and finished products. Beverage Emulsion Manufacture AC C EP TE D 857 866 Beverage emulsions are usually prepared using a two-step process: a beverage emulsion 867 concentrate (3 – 30 wt% oil) is prepared. Yamauchi. when the color changes beyond an acceptable level. The chemical degradation of 846 carotenoids leads to color fading.1 wt% oil) (Tan..3..e. Defining the End of Shelf Life SC M AN U 856 RI PT 848 The end of the shelf life of a product can be defined as the time when it becomes unacceptable to consumers. when the flavor components decompose/oxidize and 860 create an unacceptable flavor profile. 1997. was faster for a non-ionic surfactant (Tween 20) than for a protein (β- 853 lactoglobulin). and temperature) and antioxidant addition (i. They should then develop a systematic testing scheme that can be used to 864 predict the shelf life of products. pH. Xiao. ionic strength.. & McClements. & Kato. all the aqueous phase components are usually mixed 873 together and all of the oil phase components are mixed together prior to homogenization. 1993). 851 The rate of β-carotene degradation was found to increase with decreasing pH and increasing 852 temperature. EDTA and ascorbic acid) on the chemical degradation of β-carotene 850 encapsulated within oil-in-water nanoemulsions (Qian.ACCEPTED MANUSCRIPT 30 845 Woodall.. 865 6. which is then diluted extensively to create the finished 868 product (< 0. 847 Recent studies have examined the influence of interfacial properties (i. A beverage manufacture should 862 establish quantitative criteria that can be used to establish the end of the shelf life of their 863 particular product.e. and then review some of the major manufacturing 870 approaches for forming stable beverage emulsions. A product may become unacceptable when a ring of oil 859 droplets is visible at the top of the bottle. Miyake. 849 vitamin E. Inoue. and may reduce their beneficial health properties. storage conditions (i. emulsifier type). In this section. 2012). and decreased with increasing antioxidant addition to either the oil or aqueous 854 phase. et al. 2004). or 861 when the product is microbiologically unsafe to consume.e. 871 Beverage emulsion concentrates: When beverages are prepared using high energy 872 homogenization methods (see below). Decker. 855 5.

pH regulators etc. preparation conditions (e. M AN U SC RI PT 874 Finished Product: The finished product is created by diluting the beverage emulsion 889 concentrate with another aqueous phase. The final product may be homogenized again to ensure that any 893 non-polar colors. buffers. the oil phase may also have to be heated and 877 mechanically agitated to facilitate the melting and dispersion of any antioxidants. flavors. such as ringing and oiling off (see earlier section). which is then mixed with the 884 aqueous phase. etc. 904 weighting agents. This process can lead to the spontaneous formation of a microemulsion. changes in flavor 900 profile due to degradation of flavor molecules (such as citral) or color fading due to degradation 901 of colorants (such as carotenoids). e. such as 890 colors.. AC C EP TE D 888 . minerals 876 and other functional ingredients). ripening inhibitors.1 to 1 µm).. Beverage emulsions 899 are also liable to undesirable quality changes due to chemical degradation. the perceived quality of a product may deteriorate after 896 extended storage due to detrimental changes in its physical or chemical properties. weighting 878 agents. or emulsion depending on system composition and preparation procedure. and preservatives are incorporated into the oil droplets. water-soluble surfactants and some other water-soluble 883 components may initially be incorporated into the oil phase. the concentrate is diluted 500-1000 891 times to produce a final product that often has an oil concentration < 20 mg per liter for a ready- 892 to-drink product (Given. which may contain various other ingredients.g. 887 and then stored or transported to the place where it will be used. preservatives. These challenges can often be overcome using appropriate 902 packaging materials and/or proper product formation. emulsifiers. The design and formulation of successful 903 soft drink products requires careful selection of functional ingredients (oil type.ACCEPTED MANUSCRIPT 31 aqueous phase often has to be heated and mechanically agitated to facilitate dissolution and 875 dispersion of water-soluble components (such as emulsifiers. Typically. antioxidants. 885 nanoemulsion. 2009). ripening inhibitors. However. Beverage 897 emulsions are susceptible to various physical instability mechanisms that can lead to undesirable 898 changes in appearance. Similarly.g. In this case. thickening agents. After 886 preparation the beverage emulsion concentrate is often pasteurized to reduce the microbial load. Once the oil and aqueous phases have been prepared they 879 are blended together using a high-shear mixer to form a coarse emulsion (d ≈ 1 to 10 µm). or colors. flavors. When 881 beverages are prepared using low energy homogenization methods a different approach may be 882 taken (see below).). which 880 is then homogenized using a mechanical device to form a fine emulsion (d ≈ 0. Appropriate 894 selection of ingredients and processing conditions may lead to beverage products with shelf lives 895 longer than 12 months.

Low energy approaches rely on 920 the spontaneous formation of fine oil droplets within mixed surfactant-oil-water systems when 921 the solution or environmental conditions are altered (Anton. & Nakajima. high-pressure 934 valve homogenizers. & Saulnier. Pouton & Porter. Briancon. 2004).g.1. Leong. and storage conditions (e. & Solans. Wooster. Tadros.. these approaches can be categorized as either high-energy or low-energy approaches 909 depending on the underlying physical principle of droplet formation (Acosta. & Fessi. and oxygen). 2009. Kentish. High-Energy Approaches SC M AN U TE D EP AC C 929 RI PT 907 The size of the droplets generated by high energy approaches is determined by a balance 930 between two opposing processes occurring within the homogenizer: droplet disruption and 931 droplet coalescence (Jafari. High-energy approaches utilize mechanical 912 devices (“homogenizers”) that generate intense forces capable of disrupting and intermingling 913 the oil and aqueous phases leading to the formation of very fine oil droplets (Figure 9). He. et al.g.ACCEPTED MANUSCRIPT 32 905 homogenization method and operating conditions).. microfluidizers. phase inversion and spontaneous 926 emulsification methods (Figure 10). 2004. 923 Freitas.. et al. 2008. exposure to 906 elevated temperatures. 2008b). Ichikawa. Chu. 922 Bouchemal.. 2008. Assadpoor. & Bhandari. Velikov & Pelan. light. and they can be used to 919 prepare emulsions from a variety of different starting materials. Kobayashi. 917 High-energy approaches are probably the most common method used for preparing beverage 918 emulsions at present because they are capable of large-scale production. Perrier. which are highlighted in the sections below. 928 6. 2006.. i. Esquena. Kanafusa. & Nakajima. 2009. 2007. 2009). The minimum particle size that can be produced using 927 either approach depends on many different factors. Tadros. 2009. and ultrasonic devices (Leong. & Ashokkumar. In 908 general.. 911 Tadros. Anton & 910 Vandamme. 924 A number of different low energy approaches have been developed. 2009. 2008. Wooster.. Chu. The 914 most commonly used homogenizers utilized in the beverage industry for forming emulsions are 915 high pressure valve homogenizers. Only those mechanical devices 932 that are capable of generating extremely intense disruptive forces are capable of producing the 933 tiny droplets required for most beverage emulsion applications (Figure 9). 2005. et al. Yin. & Gander. et al. Izquierdo. et al. et al. and some of these are 925 suitable for utilization within the beverage industry. 2009. but microfluidizers and ultrasonic methods may also be used 916 (Gutierrez. 2004. . e. Leong.e. Merkle. 2008)... Benoit. A number of different methods can be used to form beverage emulsion concentrates.

g.g. Finally. it is usually easier to 948 produce very small droplets when the oil phase has a low viscosity and/or interfacial tension 949 (e. Once the 943 homogenization conditions have been optimized. energy intensity.. homogenizer operating 937 conditions (e.. Small droplets can only usually be produced 963 when the disperse-to-continuous phase viscosity ratio falls within a certain range (0. phospholipids. Even so. It also depends on the viscosity ratio of the two 962 phases (usually oil and water) being homogenized. and the physicochemical properties 939 of the component phases (e.05 < ηD/ηC < 964 5) (Tadros. viscosity) (Kentish. flow and force profiles). temperature). triacylglycerol 950 oils). The 955 homogenizer has a pump that pulls the coarse emulsion into a chamber on its backstroke and 956 then forces it through a narrow valve at the end of the chamber on its forward stroke (Figure 9).g. 1993. Walstra. sample 938 composition (e. concentrations). it is important to have sufficient AC C EP 953 .. 957 As the coarse emulsion passes through the valve it experiences a combination of intense 958 disruptive forces that cause the larger droplets to be broken down into smaller ones.. the size of the droplets produced depends strongly on 947 the characteristics of the oil and emulsifier used (see below). 2006. oil type. Different 959 nozzle designs are available to increase the efficiency of droplet disruption.g. For example. emulsifier type. Thus. 941 RI PT 935 High energy homogenizers are widely used to produce beverage emulsions because they can be utilized with a wide variety of different types of oils and emulsifiers. interfacial tension. duration).ACCEPTED MANUSCRIPT 33 2004). High Pressure Valve Homogenizers M AN U TE D 952 SC 942 High pressure valve homogenizers are currently the most common high-energy method of producing beverage emulsions. et al. polysaccharides.g. et 940 al.. et al. 2003). 945 or surfactants as emulsifiers. environmental conditions (e.g. 2004. and proteins.. Wooster. beverage emulsions can be produced using 944 triacylglycerol oils or flavor oils as the oil phase.1. The smallest droplet size that can be produced by a particular high-energy device 936 depends on homogenizer design (e.. a coarse emulsion is produced using a high shear mixer 954 and then this is fed directly into the inlet of the high pressure valve homogenizer..1. flavor oils) than when it has a high viscosity and/or interfacial tension (e.g.. Initially. 951 6. The droplet size 960 produced using a high pressure valve homogenizer usually decreases as the number of passes 961 and/or the homogenization pressure increases. 2008b). high-energy methods are suitable for producing both cloud 946 emulsions and flavor emulsions.

2010. & Hallett. Intense disruptive forces are generated within the interaction chamber when the two 981 fast moving streams of emulsion collide. 2005b). there is usually a linear 989 relationship between the logarithm of homogenization pressure and the logarithm of the droplet 990 diameter: log d ∝ log P.g... Henry.. et al. These studies have shown that small 985 droplets can be produced provided that conditions are optimized to facilitate droplet disruption 986 and inhibit droplet coalescence. 2008b). Even then. 1997. The droplet size tends to decrease with increasing 987 homogenization pressure.2. Klein. This study 992 showed that the logarithm of the mean droplet diameter decreased linearly with the logarithm of 993 the homogenization pressure for both an ionic surfactant (SDS) and a globular protein (β- 994 lactoglobulin) (Figure 11). Aserin. and appropriate viscosity ratios). However.1. 974 6. 2011). Svitov. 2010). high 973 emulsifier levels. 2008). 984 & Norton. there is a linear relationship between the logarithm of the homogenization 968 pressure (P) and the logarithm of the droplet diameter (d): log d ∝ log P. Frith. number of passes. and decreasing disperse- 988 to-continuous phase viscosity ratio (Wooster. Recent studies have identified some of the major factors influencing the 991 formation of fine emulsions using microfluidizers (Qian & McClements. To reduce the droplet 970 size to the level required in beverage emulsions it is sometimes necessary to operate at extremely 971 high pressures and to use multiple passes through the homogenizer. TE D 976 A number of studies have examined the potential application of microfluidizers for the 983 production of model beverage emulsions (Dalgleish. West. Microfluidizers SC The formation of beverage emulsions using a microfluidizer also involves forcing a coarse M AN U 975 RI PT 965 emulsion through a narrow orifice under high pressure to facilitate droplet disruption. Again. 977 the design of the channels through which the emulsion is made to flow within a microfluidizer is 978 different from that of a high pressure valve homogenizer (Figure 9). low interfacial tensions. with the constant of 969 proportionality depending on homogenizer type (McClements. Usually. However. emulsifier concentration. Fryer. leading to highly efficient droplet disruption. The microfluidizer divides 979 an emulsion into two streams that are then made to impinge on each other in an interaction 980 chamber. it is only 972 possible under certain circumstances to obtain droplets less than 100 nm in radius (e. 967 et al. and to 966 use an emulsifier that can rapidly adsorb to the droplet surfaces to prevent re-coalescence (Jafari.ACCEPTED MANUSCRIPT 34 emulsifier present to cover all the new droplet surfaces formed during homogenization. & Garti. the slope of the log(d) versus log(P) relationship was AC C EP 982 .

.. et al. 1999). Anton & Vandamme. A number of methods for preparing fine emulsions 1024 are based on the low-energy approach. He. which was attributed to 996 the fact that the protein may adsorb more slowly to the droplet surfaces. Maa & 1015 Hsu. Leong. et al. Wilhelm. 1999. et al. 2009). which suggested that droplet disruption 1001 within the homogenizer became easier as the viscosity of the two phases became more similar. 1005 6. 1002 On the other hand.1.. and the viscosity of the oil and aqueous phases (Jafari.. 2009. Canselier. Maa & Hsu. 1999). & Bhandari. This type of homogenizer utilizes high intensity ultrasonic waves to generate intense disruptive forces 1008 (mainly generated by cavitation) that break the oil and water phases into very small droplets 1009 (Kentish. which again may be due to the relatively slow 1004 adsorption of the protein and its ability to form a coating that inhibits further droplet disruption. 2008). Leong. 1023 Bouchemal.57) than for the protein (-0. For the ionic surfactant there was a distinct decrease in 1000 mean droplet diameter with decreasing viscosity ratio. Low-Energy Approaches EP AC C 1020 TE D 1007 The formation of emulsions using low-energy approaches relies on the spontaneous 1021 formation of oil droplets in surfactant-oil-water mixtures when either their composition or their 1022 environment is altered in a specific way (Anton. 2009). and that it may form a 997 viscoelastic coating that inhibits further droplet breakup. including spontaneous emulsification and phase inversion . Batch and continuous ultrasonic 1010 homogenizers are available for producing emulsions (Leong.29). Yin. The size of the droplets produced using these devices 1013 tends to decrease as the intensity of the ultrasonic waves is increased or the residence time in the 1014 disruption zone is increased (Abismail.ACCEPTED MANUSCRIPT 35 appreciably steeper for the surfactant (-0. Ultrasonic Homogenizers SC M AN U 1006 RI PT 995 Beverage emulsions can also be formed continuously using ultrasonic homogenizers. Kentish. The homogenization efficiency also depends on the type and amount of emulsifier 1016 present... et al. but are less suitable for more viscous systems. Delmas. et al. 1017 et al. 2006. 2004.. little change was found in mean droplet size with viscosity ratio when a 1003 globular protein was used as an emulsifier.2. 2008. However. 2006. & Gourdon.3. 2009. 1019 6. et al. The dependence of the mean droplet 998 diameter on viscosity ratio (ηD/ηC) was also examined by preparing emulsions using different oil 999 phase and aqueous phase compositions. et al. 2009. Ultrasonic homogenizers are particularly 1018 suitable for low-viscosity fluids. continuous 1011 ultrasonic homogenizers are probably the most commonly used methods for the large scale 1012 production of fine emulsions (Figure 9). 2006.. Lin & Chen.

1026 & Kuhnle. Maestro. 2009.1 wt% MCT. 2008. it is currently not possible to use proteins or polysaccharides as emulsifiers 1032 in most of the low energy approaches used to form very fine emulsions. In the 1053 low energy method.4 wt% non-ionic 1050 surfactant. et al. & Gutierrez.1. Fernandez. and then passed through a microfluidizer. et al. Some of these low 1027 energy methods are already used in the beverage industry for forming oil-in-water emulsions. Andre. with the surfactant containing a 50:50 mixture of a 1051 hydrophilic (Tween 80) and lipophilic (Tween 85) surfactant. Instead. the 1052 surfactant. In the high energy method. oil and water were blended together. The surfactant-oil-water system used consisted of 15. Sole. 1029 RI PT 1025 Low energy approaches are often more effective at producing small droplet sizes than high energy approaches. and 61. 2008). Rieger. 2006). or the aqueous phase may be titrated into the 1042 organic phase (Sonneville-Aubrun. For example. 2009. and possibly water-miscible 1039 solvent. 2004. 23. but they are often more limited in the types of oils and emulsifiers that can be 1031 used. 1988. relatively high 1033 concentrations of synthetic surfactants are usually required to form stable emulsions by these 1034 approaches. hydrophilic surfactant. Solans. the oil and surfactant were mixed together. 2012). which limit their use for some beverage applications. 2009).5% water.. The microfluidization method produced droplets with a diameter of . Miller. 1028 whereas others may also be for certain applications.2. When the two phases come into contact the 1043 hydrophilic surfactant and/or solvent move from the oil phase to the aqueous phase. Anton & Vandamme. Leser. Spontaneous Emulsification Methods M AN U 1036 SC 1030 In this method an emulsion is spontaneously formed when an organic phase and an aqueous phase are mixed together (Anton & Vandamme. 2001). and then simply titrated into the 1054 water using slow stirring. which 1044 generates tiny oil droplets at the phase boundary (Horn & Rieger. Gonzalez. Sher.ACCEPTED MANUSCRIPT 36 methods (Figure 10) (Anton. 2009). whereas the aqueous usually contains water and possibly cosolvent and cosurfactant. The size of the droplets 1045 produced can be controlled by varying the compositions of the two initial phases. as well as the 1046 mixing conditions. 1035 6. EP The spontaneous emulsification method was recently compared with a high energy method AC C 1047 TE D 1037 1048 (microfluidization) of producing fine emulsions (Yang. Pouton & Porter.. 1038 The organic phase usually contains oil. & 1049 McClements. 1040 The two phases can be brought together in various ways: the organic phase may be titrated into 1041 the aqueous phase (Anton & Vandamme. Marshall-Breton.

A transitional phase inversion occurs when the surfactant properties are altered by 1080 adjusting a formulation variable. In the PIT method the change from one type of an emulsion to another involves a 1078 transitional phase inversion.. 2004.e. The ability of fine emulsions to be formed using the spontaneous emulsification method M AN U 1065 SC RI PT 1055 depends on the system composition (surfactant. 1067 and preparation method (order of addition. et al. surfactant. such as temperature. whereas the spontaneous emulsification method could produce droplets with 1056 diameters around 140 nm. Thakur. phase inversion temperature (PIT) 1076 and emulsion inversion point (EIP) methods (Fernandez. This approach is suitable for 1068 producing flavor or cloud emulsions. oil type. AC C 1075 . mixing speeds). and requires no major 1071 equipment. These 1062 measurements show that there is a minimum in the mean droplet size at a particular SOR. provided that the system composition 1058 was optimized. surfactant type. A catastrophic phase 1081 inversion occurs when the ratio of the oil-to-water phases is altered while the surfactant properties 1082 remain constant. a much higher surfactant-to-oil 1059 ratio (SOR) is required to produce small droplets using the low energy method than with the high 1060 energy method. oil. oil.g.2. The influence of SOR on the mean droplet diameter of vitamin E nanoemulsions 1061 produced using the spontaneous emulsification approach is shown in Figure 12.. 2008).. and water levels).2. whereas the disadvantage is that relatively high surfactant levels are required (SOR ≈ 1072 1) 1073 6. Phase Inversion Methods A number of methods have been developed to formulate fine emulsions that depend on EP 1074 TE D 1066 inducing a phase inversion from a W/O to O/W form. provided that an appropriate surfactant is used (such as a 1069 non-ionic surfactant with a particular HLB number) and the surfactant-to-oil ratio is optimized. and 1063 therefore the composition of the system has to be carefully controlled to obtain a particular 1064 droplet size. e. simple. However. or ionic strength.ACCEPTED MANUSCRIPT 37 about 110 nm. and water contents. Villette. pH. whereas in the EIP method it involves a catastrophic phase inversion 1079 (Figure 13). 1070 The main advantage of this method is that it is inexpensive. i. & 1077 Delaplace. Aubry. This simple experiment demonstrated that nanoemulsions could be 1057 produced using the spontaneous emulsification method.

The driving force for this type of phase inversion is the 1092 change in the physicochemical properties of the surfactant molecules caused by temperature 1093 changes. which has also been used to interpret the PIT phenomenon (Anton. Emulsions containing very fine droplets can be 1087 spontaneously formed using the PIT method by varying the temperature-time profile of 1088 appropriate mixtures of surfactant. As the temperature is raised and the head group becomes 1112 progressively dehydrated and the solubility of the surfactant in water decreases. W/O to O/W or vice 1090 versa) through an intermediate state. Gutierrez. the head group is relatively 1107 small compared to the tail group (p > 1) and so W/O emulsions are favored.1. for p > 1 the optimum curvature is concave 1102 (favoring W/O systems). e. Upon 1104 heating.. Surfactants spontaneously associate in water to form monolayers that have a 1098 curvature that allows the most efficient packing of the surfactant molecules. p (Israelachvili. monolayers with zero curvature 1101 are preferred (favoring lamellar structures). oil. the 1100 optimum curvature is convex (favoring O/W systems). The molecular geometry of a 1094 surfactant can be characterized by a packing parameter. and water. Anton 1086 & Vandamme. The relative solubility 1108 of non-surfactants in the oil and water phases also changes with temperature because of head group 1109 dehydration. while its solubility AC C EP TE D 1097 .. and. 1105 At the phase inversion temperature (PIT). At low temperatures..2. 2009). 2011): 1096 SC p= M AN U 1095 RI PT 1083 1084 aT aH (7) where. For non-ionic surfactants. et al. the head group is relatively large compared to 1103 the tail group (p < 1) at temperatures below the PIT and so O/W emulsions are favored. the head group becomes progressively dehydrated and so the packing parameter increases.g. 2008). 2009. This intermediate state is typically a liquid crystalline or 1091 bicontinuous microemulsion phase. for p = 1. Gayet. molecular geometry and solubility (Figure 10).ACCEPTED MANUSCRIPT 38 6. 2007. Benoit. The optimum 1099 curvature of a monolayer depends on the packing parameter of the surfactant: for p < 1. 2007. Above the PIT.g. Phase Inversion Temperature Method The PIT method is based on changes in the optimum curvature and relative solubility of 1085 non-ionic surfactants with changing temperature (Anton. et al. aT and aH are the cross-sectional areas of the lipophilic tail-group and hydrophilic headgroup respectively.2. This type of phase inversion usually involves 1089 the controlled transformation of an emulsion from one type to another (e. Anton 1110 & Vandamme. the head group and tail group have similar sizes (p = 1) 1106 and so liquid crystals or microemulsions are formed. the head group is highly hydrated and so the surfactant 1111 tends to be more soluble in water. & Saulnier..

oil droplets are formed by a mechanism similar to spontaneous emulsification. This second surfactant partially displaces some of the original 1138 surfactant from the droplet surfaces.g. This 1140 approach could be used in the food and beverage industry to form very fine droplets using the PIT 1141 method. Upon cooling. Thus at high temperatures the surfactant is mainly located 1116 in the oil phase. At a particular temperature (≈ PIT). sterilization or cooking) or that are stored at 1134 elevated temperatures (e. 1118 RI PT 1113 The PIT method is relatively straightforward to implement (Figure 10). Recently. a flavor oil (10 wt% lemon oil). and then stabilizing them by diluting them in a different surfactant solution. M AN U TE D 1130 SC 1119 One of the limitations of the phase inversion temperature method is that the emulsions produced are often highly prone to droplet coalescence when they are stored at temperatures 1132 approaching the PIT. thereby altering the optimum curvature and PIT of the 1139 surfactant monolayer. as well as increasing the repulsive interactions between the droplets.ACCEPTED MANUSCRIPT 39 in oil increases. which leads to 1122 the spontaneous formation of an oil-in-water emulsion or nanoemulsion (Anton & Vandamme. and then becomes opaque when heated above 1128 the PIT due to formation of a W/O emulsion. the surfactant.. the system goes from turbid to 1129 transparent indicating that a nanoemulsion was formed (d = 45 nm). 1142 1143 AC C EP 1131 The PIT method can only be used for certain combinations of oils and surfactants. A mixture of surfactant. 1136 and then diluting the resulting emulsions in a solution containing another surfactant with a high PIT 1137 (Rao & McClements. the solubility of the surfactant in the oil and 1114 water phases is approximately equal. in warm or hot climates). Upon heating the 1127 system becomes transparent when the PIT is reached. 2010). This could be a problem in food and beverage applications that require some 1133 form of thermal treatment (such as pasteurization. we developed an approach to 1135 overcome this problem by forming emulsions using a non-ionic surfactant with a relatively low PIT. An example of the phase behavior of a SOW mixture consisting of a non-ionic surfactant 1124 (13% Tween 80). which leads to the formation of a microemulsion or liquid crystalline phase. 1123 2009). the surfactant becomes more soluble 1115 in the oil phase than in the water phase. oil and water were 1126 blended together to form a coarse O/W emulsion that was optically opaque. and when the system is cooled it has a tendency to move into the aqueous phase. somewhere . and water (SOW) is initially heated up to a temperature around or slightly above the 1120 PIT. oil. Initially.g. At higher temperatures. 1117 Thus. and water (77%) upon heating and cooling is 1125 shown in Figure 14 (Rao & McClements. The SOW system 1121 is then quench cooled to a temperature well below the PIT with continuous stirring. 2010). The PIT must be within a practical range that can be implemented within the food industry (e.

At relatively low 1159 surfactant concentrations the formation of multiple emulsions is suppressed and only relatively 1160 large oil droplets are produced in the final emulsion. which means that for many 1147 triacylglycerol oils the PIT is too high to practically reach. to an O/W/O multiple emulsion. 1150 1151 6. Innes. such as the stirring speed. & Sajjadi. 2006). SC M AN U TE D EP AC C 1170 RI PT 1144 We have recently used the EIP method to produce emulsions with relatively small droplet 1171 diameters (< 100 nm) (Ostertag. depends on process variables. The droplet size produced by this 1173 method depended on: (i) oil type: medium chain triglycerides (MCT) < flavor oils (orange and . On the other hand. The emulsifiers used in catastrophic phase 1168 inversion are usually limited to small molecule surfactants that can stabilize both W/O emulsions (at 1169 least over the short term) and O/W emulsions (over the long term). At relatively high surfactant concentrations. The aqueous phase is then slowly titrated 1155 into this organic phase with constant stirring. and 1167 the emulsifier concentration (Thakur. as well as the size of the oil droplets 1166 produced. Nevertheless. it is still important to select an 1149 appropriate type and amount of surfactant to ensure the PIT is in the correct range.2. et al. flavor oils seem to be 1148 amenable to emulsification using the PIT method. Initially. the rate of water addition. The value 1165 of the critical concentration where phase inversion occurs. and if it is 1145 too low the emulsions formed will be highly unstable to droplet growth.. multiple emulsions are 1163 formed during the titration process. As the amount of water added increases the system 1156 converts from a W/O emulsion. The formation of these multiple emulsions 1158 requires that the hydrophilic surfactant is initially located in the oil phase.2. Weiss. We titrated water into an organic 1172 phase containing a mixture of oil and water-miscible surfactant. which are similar in size to those that would 1161 be produced if the surfactant had been dissolved in the water phase prior to homogenization 1162 (Jahanzad. 1157 Crombie.2. Sajjadi. The PIT tends to increase 1146 with increasing molecular weight and hydrophobicity of oil molecules. 2009. 2008). an organic phase is 1154 prepared that contains oil and a hydrophilic surfactant. 1152 It simply involves titrating increasing amounts of an aqueous phase into an organic phase to induce 1153 a catastrophic phase inversion from a W/O to an O/W system..ACCEPTED MANUSCRIPT 40 between 40 and 90 ºC) – if it is too high then it will not be possible to create emulsions. Emulsion Inversion Point (EIP) Method The emulsion inversion point (EIP) method can also be implemented very easily (Figure 10). and the final oil droplet size within the O/W emulsions is 1164 determined by the size of the inner oil droplets in the intermediate O/W/O emulsions. 2012). 2009). et al. to an O/W emulsion (Jahanzad. & McClements.

lemon and peppermint oils.1) than the 1181 low energy method (SOR ≥ 0. the extraction procedure used to isolate them. Terenina. As an example.1. higher-fold oils have different and more intense flavor 1201 profiles than lower-fold oils. (ii) surfactant 1175 type: Tween 80 < Tween 20 < Tween 85. since the 1185 beverage emulsion concentrates are diluted so much. The composition of natural flavor oils depends on their biological 1192 origin. three-fold (3×). while those that have undergone further processing (such as distillation) are referred to as 1199 higher fold oils e.ACCEPTED MANUSCRIPT 41 limonene) < long chain triglycerides (olive. and it may then be 1194 further refined using steam distillation and various other methods (Misharina. Beverage Emulsion Ingredients 1187 7. Flavor Oils SC M AN U TE D 1189 RI PT 1174 Flavor oils. peanut and canola oils). lemon oil is usually obtained from lemon peel by cold pressing. For 1193 example. The EIP method was also compared to a 1179 high energy method (microfluidization). five-fold (5×). since they contain volatile constituents with 1191 characteristic aroma profiles. Commercially. & Cabral. Oil Phase Components 1188 7. & Medvedeva. and any subsequent processing steps. Normally. (iv) surfactant location: surfactant initially in oil < 1177 surfactant initially in water. Flavor oils extracted by cold pressing are usually referred to as single-fold (1×) 1198 oils. Small droplets (d < 160 nm) could be produced by both 1180 methods.. 1186 7.1. the data for the influence of oil type on droplet size 1178 produced using the EIP method is shown in Figure 15. (iii) surfactant concentration: smaller droplets were 1176 produced at higher surfactant-to-oil ratios (SOR). Sakanaka. In 1184 the finished product. Differences in the chemical composition of flavor oils also leads to AC C EP 1190 . 1195 Krikunova. grape. flavor oils are available in various forms 1196 (“folds”) that differ in chemical composition due to differences in isolation and processing 1197 procedures used.7). 2006). or ten-fold (10×) oils (Gamarra.g. 2010). sesame. but that much less surfactant was needed for the high energy method (SOR ≥ 0.1. the levels of surfactant may be quite small (even when SOR ≈ 1). are widely used in the food and beverage industries as flavoring agents. provided that having relatively high amounts of surfactant present is not a problem. The EIP method may therefore be suitable for producing fine 1182 emulsions suitable for use in the beverage industry without the need for expensive homogenization 1183 equipment. such as orange. 1200 Tambourgi.

nanoemulsions and emulsions (Rao & 1207 McClements. & Yusof. which was attributed to the presence of 1220 an appreciable fraction of low water-solubility constituents that acted as “ripening inhibitors” 1221 (see later). Rao & McClements.. Emulsions produced using lower fold oils (1×. For example. presumably because they contained constituents that 1223 more easily fit into micelle structures. et al. et al. 2012b. 2012c).. citral decomposes rapidly during storage at acidic pH by a series of 1232 cyclization and oxidation reactions (Choi. The main constituents in 1209 1× lemon oil were monoterpenes (> 90 %).ACCEPTED MANUSCRIPT 42 differences in their physicochemical properties (e.g. the lower fold oils were more suitable for forming 1222 microemulsions than the higher fold oils. 2011. interfacial tension. Rao & McClements.. 3×. Many flavor oils used in beverage emulsions are unstable to chemical degradation during 1231 storage. 2008. viscosity. sesquiterpenes (≈ 14%) and oxygenates (≈ 33%). 2009). while intermediate polar 1212 components decreased.. addition of antioxidants (Yang. Tan. Rao & McClements.. presence 1229 of surfactant micelles (Choi. 1230 2010). 5× and 10×) on the 1206 formation and properties of oil-in-water microemulsions. On the other hand.e. 1203 refractive index. SC M AN U TE D EP A number of recent studies have examined the major factors influencing the formation and AC C 1224 RI PT 1202 1225 stability of beverage emulsions containing flavor oils. In recent studies. emulsifier type (Mirhosseini. and refractive index of the 1213 lemon oils increased as the oil fold increased (i. viscosity. Qian & McClements. Mirhosseini. the diffusion 1218 of water-soluble lemon oil components from small to large droplets. et al. 2011). density. . The density..e. et al. droplet charge (Choi. Hamid. 1228 2011). 2010a). with the growth rate increasing with increasing storage temperature and 1217 decreasing oil fold. The stability of oil-in- 1214 water emulsions produced by high pressure homogenization was strongly influenced by lemon 1215 oil type. 1227 Tan. and the physical state of the oil phase (Mei. et al. 2012a. 5×) were highly unstable to droplet 1216 growth during storage. molecular characteristics. Droplet growth was mainly attributed to Ostwald ripening i. which influences their ability to form and stabilize 1204 beverage emulsions (Rao & McClements. The concentration of 1211 both polar and non-polar components increased with increasing oil fold. including the preparation method used 1226 (Cheng & McClements. 2010b). Emulsions prepared using 1219 the highest fold oil (10×) were stable to droplet growth. 3×. The composition. whereas the major constituents in 10× lemon oil were 1210 monoterpenes (≈ 35%). 1205 our laboratory has examined the influence of lemon oil fold (1×. 2008. 1208 and physicochemical properties of the four lemon oils were tabulated. 1× < 3× < 5× < 10×).. 2012c).. et al.. 2011. and optical properties). water solubility. 2012c). Aghlara. This effect is highlighted in Figure 16.

Cloud Oils AC C EP TE D M AN U SC RI PT 1233 1259 The oil droplets in cloud emulsions are composed mainly of non-flavor oils. et al.g. 2003). Choi. when citral is located predominantly within a non-polar 1246 environment. Triacylglycerol oils are typically derived from natural sources 1261 such as vegetable. 2004b.ACCEPTED MANUSCRIPT 43 which shows the amount of citral remaining in aqueous solution during storage at different pH 1234 values: the degradation rate increases rapidly as the pH is decreased. On the other hand. This phenomenon may be important for beverage emulsion concentrates that have relatively 1252 high fat contents. oil. This effect is highlighted in Figure 17. For example. water. et al..1..2. rather than the aqueous phase. such as the interior of a lipid droplet or surfactant micelle. & Ho. 2009. it is possible to reduce its degradation rate by altering its partitioning between the oil 1245 and aqueous phases. canola and sunflower oils.. e. If a labile component is located within an environment where it 1242 is isolated from other components that promote its chemical degradation. since in this case an appreciable fraction of the citral will be present within the 1253 oil phase. it is partially protected 1247 from degradation. These oils have very low water-solubilities and are therefore . Ueno. It also depends on the 1240 location of the citral molecules within an emulsion. & Masuda. corn. Citral degradation reduces 1235 the level of desirable aroma compounds present as well as increasing the levels of undesirable 1236 aroma compounds. 1249 This effect can be attributed to the fact that a lower fraction of the citral is present within the 1250 acidic aqueous phase as the fat content increases due to equilibrium partitioning effects (Figure 1251 18). such as temperature. Ueno. once an emulsion concentrate is diluted to form the finished 1256 product nearly all of the flavor molecules partition into the aqueous phase and therefore any 1257 protective effect is lost. 2006.. will then help to inhibit citral degradation 1255 during storage. Liang.. Wang. thus limiting the shelf life of many beverages. The rate of citral degradation 1237 in emulsions is affected by environmental and compositional factors. then it is possible to 1243 reduce the degradation rate. Ho. whereas terpene oils are usually isolated by 1262 distillation of natural flavor oils. 1238 oxygen availability. 1241 et al. 2009. 1258 7. et al. or interfacial regions (Choi. Choosing an oil type and concentration that ensures that most of the citral is present 1254 within the oil droplets. 1239 2004a. Since citral degradation occurs predominantly in acidic aqueous 1244 solutions. Kiyohapa. 2010b). Simon. such as 1260 triacylglycerol or terpene oils. which shows that the rate of citral 1248 degradation in oil-in-water emulsions decreases as the total fat droplet concentration increases. and antioxidant addition (Choi.

it may be necessary to use an oil 1282 phase that remains liquid at refrigerator temperatures (e. water.. conjugated linoleic 1286 acid. winterized or fractionated oil). and headspace regions (McClements. carotenoids. The melting 1278 characteristics of cloud oils may also be important for certain applications since partially 1279 crystalline oil droplets are susceptible to partial coalescence leading to droplet aggregation and 1280 phase separation (McClements. with higher viscosities normally 1276 leading to larger droplets. 2009)..g. Decker. Each type of nutraceutical lipid has its own particular 1291 challenges depends on its physicochemical properties. and may therefore influence their long-term stability. 2005b). such as polyunsaturated fats. the 1272 oxidation of unsaturated lipids products rancid off-flavors. it is also important that 1267 the droplets remain physically and chemically stable during storage.3. The incorporation of nutraceutical lipids into 1289 commercial beverage emulsions is often challenging because they are prone to various physical 1290 or chemical degradation mechanisms. 2005b). The main purpose of cloud oils is to produce 1264 droplets that scatter light strongly so as to give a product a desirable turbid or cloudy appearance. such as solubility. 1283 7. oil-water partition 1292 coefficient. Nutraceutical Lipids EP 1284 TE D 1274 There has been growing interest in the incorporation of various kinds of nutraceutical lipids into commercial food and beverage products. 1265 and so it is important that the droplets are within the size range where efficient light scattering 1266 occurs (typically around 200 to 500 nm). but they 1269 may indirectly influence flavor due to their effects on the partitioning of flavor molecules 1270 between the oil. transport. and handling. Park.ACCEPTED MANUSCRIPT 44 stable to Ostwald ripening (unlike flavor oils). AC C 1285 . In this case. They may also adversely 1271 affect the flavor profile of a beverage if they are susceptible to chemical degradation. 1268 Cloud oils do not usually contribute directly to the flavor profile of beverage emulsions. e.g. & Weiss. melting point. This may be particularly important for beverages that 1281 are stored in a refrigerator for prolonged periods. SC The physicochemical properties of cloud oils may also play an important role in the M AN U 1273 RI PT 1263 formation and stability of cloud emulsions. The density of cloud oils determines the creaming velocity of the 1277 droplets within an emulsion. and chemical stability (McClements. These nutraceutical lipids are either 1287 mixed with the other oil phase components prior to homogenization or they are encapsulated 1288 separately and then introduced intro the product.1. The viscosity of cloud oils will influence their ability 1275 to form small droplets during the homogenization process. For commercial applications. and fat-soluble vitamins. phytosterols.

. Waraho. and poor infant development (Orchard. 1319 1320 7. 2010. Waraho. immune response disorders. 1307 Pan.3. PUFAs are extremely susceptible to oxidative deterioration. A more detailed discussion of the chemical stability of PUFA was 1318 given in an earlier section. et al. 18:3). 1310 However. Bibiloni. mental disorders.3.. 2004. PUFAs are normally 1303 incorporated into foods as part of triacylglycerol molecules. Siddiqui. 2000. Reed. or phospholipids. This has prompted 1308 food manufacturers to attempt to fortify their products with ω-3 fatty acids at levels sufficiently 1309 high to have a beneficial biological effect (McClements & Decker. Polyunsaturated Lipids There has been growing interest in the incorporation of polyunsaturated fatty acids (PUFAs). SC M AN U TE D The oxidation of ω-3 fatty acids in emulsions involves a complex series of chemical EP 1312 RI PT 1293 reactions that results in the production of rancid off-flavors. et al. 1295 1296 7. including cardiovascular 1306 disease. 1297 and especially omega-3 (ω-3) fatty acids. into food and beverage products because of their 1298 potential health benefits (Ruxton. The most common ω-3 fatty acids in food 1301 oils are α-linolenic acid (ALA. including 1315 control of initial ingredient quality. & Jackson.1. 1299 2004). 2012. eicosapentaenoic acid (EPA. & Pons. removal/deactivation of pro-oxidants (such as oxygen or 1316 transition metals). 1317 2000.1. Ing. 2011). addition of anti-oxidants. McClements. Weiss. 2007. which causes problems 1311 for the long-term storage of these products (Arab-Tehrany. diacylglycerols. 20:5) and docosahexaenoic 1302 acid (DHA.. & Decker.1. 22:6). Fat Soluble Antioxidants Lipophilic antioxidants can be incorporated into the oil phase of oil-in-water emulsions to 1321 inhibit the oxidation of encapsulated chemically labile substances (such as ω-3 oils or 1322 carotenoids). but they may also be incorporated as 1304 monoacylglycerols. AC C 1313 . Omega-3 fatty acids are unsaturated fatty acids that have a double bond that is three 1300 carbon atoms from the methyl end of the molecule. & Millington. and interfacial engineering (McClements & Decker.2. Sureda. 2011).ACCEPTED MANUSCRIPT 45 Beverage products must therefore be carefully formulated taking into account the potential 1294 problems associated with the specific types of nutraceutical lipids present. Cheek. 2012). Tur. 2012). Consumption of adequate amounts of ω-3 1305 fatty acids has been linked to decreased risks of various diseases.. The control of lipid oxidation often 1314 requires a combination of different approaches to achieve adequate long-term stability. thereby extending product shelf life (Boon. et al. et al. Simpson. with EPA and DHA being the most bioactive.

ACCEPTED MANUSCRIPT 46 McClements & Decker. Lethuaut. although other health benefits 1340 have been claimed. Traber. Waraho. they can be encapsulated as 1324 functional food components themselves so as to make an “antioxidant” claim on a product label. The recommended daily intake (RDI) of Vitamin E 1349 is 15 mg/day (Gonnet. 2000.3. BHT.of. 1344 and utilization of commercial products (Gawrysiak-Witulska. 1992).g.3. E. vitamin E acetate (rather than vitamin E) is used in many 1346 food and beverage applications since it has a higher oxidative stability. The major biological 1339 function of Vitamin E appears to be as an oil-soluble antioxidant. 2010).1. For these reasons. The addition of these antioxidants typically 1329 increases the lag phase of the oxidation reaction.. 2008). storage. and rosemary extracts (McClements & Decker. & Nogala-Kalucka. et al. A number of previous . pharmaceutical. 1325 Some commonly used lipophilic antioxidants utilized within the food industry include alpha- 1326 tocopherols. Instead. and cosmetic preparations. The term “vitamin E” actually refers to a group of fat-soluble vitamins that are 1337 widely used as functional ingredients in food. and curcumin) into food 1333 and beverage products to improve their nutritional value (Sagalowicz & Leser. 2008). 1330 1331 7. carotenoids. 1350 AC C EP TE D M AN U SC RI PT 1323 Vitamin E is a highly lipophilic molecule that cannot be directly dispersed into aqueous 1351 solutions (Sagalowicz & Leser. phytosterols. 1343 2010). D. ascorbyl palmitate. Institute. Velikov & 1334 Pelan. & Boury. 2011). & Beckman. BHA. In this section. 1332 and K) and nutraceuticals (e. 2000).. et al. 2011). et al. 2009). 1327 2008). there 1342 has been interest in fortifying many foods and beverages with Vitamin E (Sagalowicz & Leser. 1345 Yoon & Choe. et 1341 al. 2009.. For this reason. including reducing cardiovascular disease. diabetes. 2010.. Alternatively. 2010). it must be incorporated into an appropriate 1352 colloidal delivery system prior to dispersion (Gonnet. Siger. 2011. flavonoids. with α- 1338 tocopherol being the most biologically active form (Chiu & Yang.Medicine. Weng-Yew & Brown. 2008. Fat Soluble Vitamins There is considerable interest in incorporating various types of fat-soluble vitamins (A. 2010. we use recent studies on the incorporation of vitamin E into 1335 emulsions to demonstrate some of the potential benefits and challenges associated with its use in 1336 beverages. and cancer (Sylvester. After consumption 1347 vitamin E acetate is broken down to vitamin E in the gastrointestinal tract by the action of 1348 pancreatic esterases (Brisson. These five molecules act as free radical scavengers and they each have the ability to 1328 absorb two free radicals before becoming inactive.. Frei. Vitamin E is unstable to oxidation and may therefore be lost during processing.

Wang. Carotenoids Carotenoids are a diverse group of lipophilic compounds that contribute to the yellow. Zhang. et al. However. Carotenoids containing oxygen are 1368 known as xanthophylls (e. Shi. pH. nanoemulsions (Hatanaka. which would make beverages particularly suitable delivery 1362 systems for this type of nutraceutical lipid. Haila. Luca. et al. 2011. lutein and zeaxanthin) while those without oxygen are known as 1369 carotenes (e. & Yueming. making them crystalline AC C EP TE D M AN U SC RI PT 1353 . Indeed. 1359 Montaldo. Encapsulation of vitamin E 1357 has been reported to improve its physicochemical stability during storage and its biological 1358 activity after consumption (Cortesi. Ribeiro. 2005). The carotenoids have been proposed to exhibit several 1370 potential health benefits: lutein and zeaxanthin may decrease age related macular degeneration 1371 and cataracts (Stringham & Hammond. Li. 2010. they become highly unstable to degradation once 1374 they are isolated. & Nastruzzi. & Liu. 2005). studies have suggested that the oral bioavailability of 1360 Vitamin E is increased when it is delivered in colloidal form rather than in bulk form (Feng. et al. 2005). such as microemulsions (Chiu & Yang. & 1377 Schubert. 1997. and that have also been claimed to have some health 1366 benefits. & Liu. 2002.g. 2004. Bourgaux. 2010)... Carotenoids are relatively stable to chemical degradation when they are 1373 present in their natural environment. 1375 Kakuda.g. Carosio.1. Lampi. dispersion of carotenoids into ingredient systems 1376 can result in their rapid degradation (Heinonen. 2009a). becoming susceptible to light. Zuccari. Ax.. 1356 2012) and emulsions (Chen & Wagner.. and temperature (Xianquan.3. Shukat. Consequently. 1363 1364 7. & Orienti. Isomerization reactions might 1380 actually be beneficial since cis isomers of carotenoids such as lycopene are thought to be more 1381 bioavailable and bioactive (Schieber & Carle. 1355 2009b). Fini. 1365 orange and red colors of many foods. Gonnet. Carotenoids can be degraded by reactions that cause the loss of double bonds 1378 or scission of the molecule. They are polyenes consisting of 3 to 13 conjugated double bonds and in some cases 6 1367 carbon ring structures at one or both ends of the molecule. & Piironen. Esposito. 1992. oxygen. An additional challenge to using 1382 carotenoids as ingredients in functional foods is their high melting point. Zhang. lycopene may decrease the risk of prostate cancer 1372 (Basu & Imrhan. lycopene and β-carotene). the double bonds in carotenoids can undergo 1379 isomerization to the cis configuration (Xianquan.. Feng. & Relkin. 1361 Wang. Wang. 2007). 2005). 2005).4. et al. 2003). Wang. In addition.ACCEPTED MANUSCRIPT 47 studies have shown that vitamin E can be successfully incorporated into emulsion-based delivery 1354 systems.

they need to be either suspended or emulsified.5. The intestinal absorption of 1393 phytosterols is very low and so dietary phytosterols do not have adverse effects on health. M AN U SC RI PT 1383 Incorporation of phytosterols and phytostanols into aqueous-based beverages is particularly 1395 difficult due to their low-water solubility. & 1404 Decker. 1999. 1405 At present. Juntunen. margarine and spreads) where 1400 solublization and dispersion within the oil phase were relatively simple. which is mainly 1390 attributed to their ability to inhibit the absorption of dietary cholesterol (Ostlund. Some of . it is unclear whether oxidized forms of phytosterols lose their bioactivity or have 1406 some toxicity as has been observed for oxidized cholesterol. 2007. Dutta. 2000). Alli.1. low-oil solubility. 1997. Intake of 1. Kandansamy & Somasundaram. and β-carotene (Gibbs. Soupas.ACCEPTED MANUSCRIPT 48 at food storage and body temperatures. Cercaci. Pizzale. Kermasha. 2004). Wrolstad & Culver. 2003. 1409 7. 2012. Phytosterols Phytosterols and phytostanols are a group of bioactive lipids derived from plants that have 1387 been shown to be have biological activity (Chaiyasit. 1401 introduced into aqueous-based foods.g. 2012).3. 2003. & Uusitupa. Elias. the phytosterol esters are hydrolyzed by 1398 enzymes in the gastrointestinal tract to produce free fatty acids and phytosterols. A more detailed discussion of the factors governing the 1384 chemical degradation of carotenoids was given earlier. After consumption. McClements. & Conte. Some of these problems have been overcome by esterification of phytosterols 1397 with polyunsaturated fatty acids. 2004.4. Phytosterols and phytostanols must 1407 therefore be encapsulated in delivery systems that will maintain their physical and chemical 1408 stability in beverage emulsions. high melting point. & Piironen. The 1388 fortification of foods and beverages with these components has become popular due to their 1389 ability to decrease total and low density lipoprotein cholesterol in humans. Sarkkinen. and tendency to 1396 form crystals.. 1385 1386 7. 1391 2001).1. & Decker. Lampi. Cordaro.6 g phytosterols/day results in an approximately 10% reduction in LDL 1392 cholesterol (Hallikainen. Rodriguez-Estrada. Lercker. Lambelet. including paprika. et al. 2007). & 1412 Mulligan. 1402 Phytosterols are also susceptible to chemical degradation (oxidation) during storage 1403 (Bortolomeazzi. Wong. lycopene. Fat Soluble Colorants 1410 For phytosterols to be AC C EP TE D 1394 A number of natural fat-soluble compounds have intense colors and can therefore be used as 1411 pigments in foods. The initial 1399 applications of phytosterols were in high fat foods (e.

. et al. the carotenoids discussed earlier (Qian. It is 1416 therefore important to establish the mechanism of chemical degradation for each type of fat 1417 soluble colorant used in a beverage product and to determine the major factors affecting its 1418 degradation (such as pH.2. which leads to a 1426 reduction in the interfacial tension thereby facilitating further droplet disruption. 2012). 1420 7. et al. Mechanism of Action SC Emulsifiers are surface-active molecules that are used in emulsions to facilitate droplet M AN U 1422 RI PT 1413 breakup within the homogenizer (thereby forming smaller droplets) and to prevent droplet 1424 growth after formation (thereby increasing long-term stability) (McClements.2. There are a number of 1435 food-grade emulsifiers that fulfill these requirements. pro-oxidants) so that an effective delivery system can be 1419 designed to ensure appropriate product shelf-life. Emulsifiers 1421 7. emulsifiers absorb to the oil-water interface. but they differ considerably in their 1436 effectiveness at forming and stabilizing beverage emulsions. The performance of an emulsifier can be characterized by plotting the . 2005b). light.. e. During homogenization. Many colorants from natural sources are highly unstable and may chemically degrade and 1415 fade rapidly during storage. 1425 1999). 1437 7. 1433 (3) the adsorbed emulsifier molecules must form a coating that prevents the droplets from 1434 coming into close proximity and merging together (McClements. 2005b.2. Once they have 1427 adsorbed to the droplet surface the emulsifiers should prevent the droplets from coalescing with 1428 each other. and may therefore be used as nutraceutical lipids 1414 also. and. Factors Influencing Selection 1438 AC C EP TE D 1423 Emulsion Formation: Two of the most important factors to consider when selecting an 1439 appropriate emulsifier for forming a beverage emulsion is its ability to produce small droplets 1440 during homogenization. Stauffer. oxygen. 2005b). An effective 1429 emulsifier system should meet a number of criteria to prevent droplet coalescence within the 1430 homogenizer (Jafari. 2008): (1) the emulsifier molecules must be present at a sufficiently 1431 high concentration to cover all of the oil-water surface formed: (2) the emulsifier molecules must 1432 form a coating around the droplet surfaces faster than the droplets collide with each other. which means they must for a protective coating around the oil droplets.g.2.ACCEPTED MANUSCRIPT 49 these components also have biological activity.1.. and the minimum amount of emulsifier required to form a stable system 1441 (McClements.

1453 and c′S is the concentration of emulsifier in the aqueous phase (kg m–3). the droplet size could be reduced further by 1463 increasing the homogenization pressure to that smaller droplets are produced. and so they tend to coalesce with 1457 each other and form larger droplets under they are covered and protected from coalescence. but the disruptive energy generated by the 1460 homogenizer is insufficient to form any smaller droplets. and. decreasing interfacial tension. (ii) the amount that they reduce the interfacial tension after 1468 absorption. Γ is the surface load of the emulsifier at saturation (kg m–2). rather 1462 than by the emulsifier concentration. the droplet size is 1461 therefore limited by the maximum disruptive energy that the homogenizer can generate. and duration (McClements. φ is the disperse phase volume fraction (dimensionless). 1458 TE D 1452 In the homogenizer-limited region there is more than enough emulsifier present to cover all of the droplets formed by the homogenizer. 2007). The 1466 most important physical characteristics are: (i) the rate at which they absorb to the oil-water 1467 interface during homogenization. . (iii) the amount required to cover a unit area of interface (surface load). In this region. 1469 Typically. and decreasing surface load. The minimum size of the stable droplets 1450 that can be produced in this region is given by (McClements. In this region. energy input. AC C EP 1459 1464 Emulsifiers differ in the abilities to form small droplets and in the amounts required to form 1465 stable emulsions due to differences in their molecular and physicochemical characteristics. A 1444 typical dependence of mean droplet diameter on emulsifier concentration for oil-in-water 1445 emulsions produced using a high pressure homogenizer is shown in Figure 19. such as homogenizer type. In this region. 2007): 1451 SC 6 ⋅ Γ⋅ φ 6 ⋅ Γ⋅ φ = cS c'S (1 − φ ) (8) M AN U d min = RI PT 1442 Here. This equation shows 1454 that the droplet size should by linearly related to the inverse of the surfactant concentration in 1455 this region. 1447 In the emulsifier-limited region the droplet size decreases with increasing emulsifier 1448 concentration and the size of the droplets is primarily limited by the total amount of emulsifier 1449 present (rather than by homogenization conditions). These curves can 1446 be divided into two regions: an emulsifier-limited region and a homogenizer-limited region. cS is the concentration of emulsifier in the emulsion (kg m–3). the homogenizer initially produces small droplets but there is 1456 insufficient emulsifier present to completely cover them all.ACCEPTED MANUSCRIPT 50 mean droplet diameter versus emulsifier concentration under standardized homogenization 1443 conditions. the size of the droplets produced under standardized conditions tends to decrease with 1470 increasing absorption kinetics.

whereas polysaccharide-coated droplets are stable across the whole 1501 pH range due to their thick adsorbed layers. The protein-coated droplets tend to aggregate near their isoelectric point 1500 due to their low net charge. or they have to be used at high levels. 1475 pH range. 2002b. The stability characteristics of a particular 1490 emulsifier are largely determined by its influence on the colloidal interactions operating between 1491 oil droplets (McClements. and mechanical abuse). but tend to flocculate at high ionic strengths or pH values close to their isoelectric point 1480 (McClements. 2010).. many globular 1478 proteins form stable emulsions at low ionic strengths and pH values far from their isoelectric 1479 point. & 1488 McClements. such as gum arabic and modified starch.ACCEPTED MANUSCRIPT 51 Emulsion Stability: The nature of the emulsifier used to form a beverage emulsion has a 1472 pronounced influence on its physical and chemical stability. 2004). ionic strengths. polysaccharides and non-ionic surfactants tend to form thick 1494 hydrophilic interfacial layers that mainly stabilize droplets through steric repulsion. temperature range. Xiao. In addition. et al. An example of 1497 differences in the electrical characteristics and aggregation stability of emulsions stabilized by a 1498 protein (whey protein isolate) and two polysaccharides (gum Arabic and modified starch) are 1499 shown in Figure 20.. On the other hand. Globular proteins and ionic surfactants tend to form thin 1492 interfacial layers that mainly stabilize droplets against aggregation through electrostatic 1493 repulsion. 1476 which is likely to be highly product specific. 2005b). Emulsifiers may vary considerably in their ability 1477 to form stable emulsions under different environmental conditions. Emulsions 1495 stabilized by electrostatic interactions are particularly susceptible to environmental changes that 1496 alter the magnitude or range of the electrical charge. and 1487 temperatures (Chanamai & McClements. tend to be have good 1486 stability to droplet aggregation across a wide range of pH values. However. Emulsions stabilized by 1485 amphiphilic polysaccharides. AC C EP TE D M AN U SC RI PT 1471 . Charoen. ionic composition. Emulsions 1482 stabilized by some types of non-ionic surfactants are also unstable at elevated temperatures (Rao 1483 & McClements.g. Decker. 2011).g. in this case because the rate of droplet coalescence increases when the 1484 surfactant approaches its phase inversion temperature (PIT). pH and ionic strength. they tend to flocculate when heated above their thermal 1481 denaturation temperature due to an increase in droplet surface hydrophobicity. these emulsifiers are often not very efficient at producing small 1489 droplets. and so beverage manufacturers must 1473 carefully select an emulsifier with appropriate stability characteristics. For example. Qian. 2011. When selecting an 1474 emulsifier it is important to establish the set of conditions that it is expected to work under (e. solvent composition. e.

2009). Natural ingredients often have a higher 1507 price than synthetic ingredients. 1524 senegal as the “gold standard” (Reiner. 1511 7. the vast majority of commercial beverage 1514 emulsions are made with a limited number of emulsifiers. Jayme. there has been increasing interest within the 1505 food and beverage industry in replacing synthetic ingredients with natural alternatives so as to 1506 create product labels that are more consumer-friendly. The 1528 hydrophobic polypeptide chain is believed to anchor the molecules to the droplet surface. gum arabic (also known as gum acacia) is probably the most widely 1520 used emulsifier in the beverage industry to formulate cloud and flavor emulsions (Given. polysaccharides. 1521 Tan. However. Phillips & Williams. and classify them according to the nature of the 1517 molecules involved (i.1. 2009. 1509 In the following sections. Ingredient Examples SC In principle.ACCEPTED MANUSCRIPT 52 Legal and Labeling Requirements: Traditionally. proteins. In this section. 1522 especially Sudan (Buffo. 2000). 2002).2. we provide a brief overview of some of the synthetic and natural 1510 emulsifiers that are currently available for use in beverage emulsions. we provide an overview of both currently used and potential emulsifiers 1516 that can be utilized in beverage products. and poorer functional performances. Polysaccharide-based emulsifiers Gum Arabic: Currently. Reineccius. 2004). Acacia senegal consists 1525 of at least three high molecular weight biopolymer fractions. but the beverage industry generally acknowledges A. 1999. & Gee. or surfactants). mainly gum arabic and modified 1515 starch. & Oehlert. The AC C EP TE D 1513 .3.3.. In practice. 2010). Dunstan. It has been proposed that the 1526 surface-active fraction consists of branched arabinogalactan blocks attached to a polypeptide 1527 backbone (Dickinson. & Peppard. but with some contribution from electrostatic repulsion also. Exudates from Acacia seyal and senegal 1523 have both been approved for use in food. Gum arabic is a natural exudate harvested from acacia trees in sub-Saharan Africa. many different kinds of emulsifiers can be used to stabilize the oil-in-water M AN U 1512 RI PT 1502 emulsions used in the beverage industry. 2003.e. 1518 1519 7.2. The change from artificial 1508 to natural food components can also increase manufacturing costs and reduce product shelf-life. The interfacial 1530 layer formed by gum arabic is believed to provide stability against droplet aggregation mainly 1531 through steric repulsion. Reineccius. many of the emulsifiers used in food and 1503 beverage applications were synthetic small-molecule surfactants due to their low cost and high 1504 efficiency (Kralova & Sjoblom. while 1529 the hydrophilic carbohydrate blocks extend into the surrounding aqueous phase.

while the hydrophilic starch chains protrude into 1558 the aqueous phase and protect droplets against aggregation through steric repulsion. 0 to 25 mM CaCl2) and 1561 temperature (30 to 90 ºC) (Chanamai & McClements. Qian. which means that it has to be used at relatively high concentrations to form stable 1540 emulsions.g. Gum arabic has a high 1548 water-solubility and a relatively low solution viscosity compared to other gums. 1995b). Kim. 1996. such as modified starch and 1546 various proteins (Chanamai & McClements. gum arabic has a 1538 relatively low affinity for oil-water interfaces compared to most other surface-active 1539 biopolymers. which facilitates 1549 its application as an emulsifier. & Schenz. ionic strength (0 to 500 mM NaCl. starches can be chemically modified to make 1552 them effective emulsifiers by attaching non-polar chains along their backbones (Trubiano. it has been shown that gum arabic-coated oil droplets 1535 remain stable to flocculation when exposed to a wide range of environmental conditions.. 2001.. Chanamai 1534 & McClements. Tan. as much as 20 % gum arabic may be required to produce a stable 12 1541 wt% oil-in-water emulsion (Tse & Reineccius. beverage 1543 emulsions. Trubiano. modified starch has a relatively low interfacial activity (compared to AC C EP 1551 . 2002b). et al. 1995a). 1547 Morr. e.ACCEPTED MANUSCRIPT 53 influence of a variety of processing conditions on gum arabic functionality has been examined 1533 (Buffo & Reineccius. which has led many food scientists to investigate 1545 alternative sources of biopolymer emulsifiers for use in beverages. 1998. 1999. Charoen. It consists primarily of amylopectin that has been 1556 chemically modified to contain a side-group that is anionic and non-polar. pH 1536 (3 to 9). For this reason. Nevertheless. 1554 One of the most commonly used modified starches is an octenyl succinate derivative of waxy- 1555 maize (Stauffer. Charoen. 2011. Because the 1559 dominant stabilizing mechanism is steric repulsion. 2011. In addition.. 2002b..g.. Garti. Charoen. et al.. 0 to 25 mM CaCl2) and thermal treatment (30 to 90 1537 ºC) (Chanamai & McClements. 2002b. 1562 2011). For example. 2011). et al.. 2002a. 1999. ionic strength (0 to 100 mM NaCl. Buffo. et al. These types of modified starch are widely used as emulsifiers in the beverage industry. et al. et al. SC M AN U TE D 1550 RI PT 1532 Modified Starch: Natural (unmodified) starches have poor surface activity due to their hydrophilic glucose backbones. 2011. Reineccius. 2001. & Oehlert. Buffo. emulsions stabilized by modified starch are 1560 resistant to changes in pH (3 to 9).. 1553 1995b). Trubiano. Like gum arabic. These side-groups 1557 anchor the molecule to the oil droplet surface. e. 1995a). 2002. Qian. For example. Nevertheless. its application as an 1542 emulsifier is restricted to products that have relatively low droplet concentrations. frequent problems have been reported in obtaining reliable sources of 1544 consistently high quality gum arabic.

. 1590 The origin of this effect is believed to be due to the pectin having some protein molecules 1591 associated with it. Nevertheless. it may promote depletion 1571 flocculation (Chanamai & McClements.ACCEPTED MANUSCRIPT 54 proteins or surfactants). 1995a). Nakauma. cellulose can be physically. et al. 2011). it is had been recommended that a 1:1 mass ratio 1565 of modified starch to oil was required to produce a stable oil-in-water emulsion (Tse & 1566 Reineccius. 2003). 2008). Studies have shown that if the concentration of non-adsorbed modified starch 1570 in the aqueous phase surrounding the oil droplets is too high. AC C EP 1580 1588 Certain types of pectin have been shown to be surface active molecules that can able to 1589 stabilize oil-in-water emulsions.. There has been debate about the molecular origin of the surface activity of these 1577 polysaccharides. In addition. or enzymatically modified to produce food-grade ingredients that have interfacial 1582 activity and can be used as emulsifiers (Garti. These 1584 ingredients are all non-ionic polymers that are soluble in cold water. Cellulose is not a good emulsifier in its natural state because it forms strong intermolecular TE D 1579 hydrogen bonds. such as methyl cellulose (MC). beet pectin (Jung & Wicker. and about whether their ability to stabilize emulsions is primarily due to their 1578 surface activity or their ability to thicken the aqueous phase (Dickinson. 2001). et al. which may be beneficial in a 1587 number of beverage emulsion applications. pectin molecules usually have a relatively high negative . 1583 hydroxypropyl cellulose (HPC). 2011. 1581 chemically.g... and so a large excess must be added to ensure that all the droplet 1564 surfaces are adequately coated. et al. there have recently been technical advances in the 1567 manufacture of modified starches that have led to emulsifiers that can be used at much lower 1568 levels (1:5 mass ratio) to form stable emulsions with small droplet sizes (Charoen. They 1586 have good stability to pH (2 – 11). 1569 Qian. et al. Modified starches usually come in powdered or 1572 granular forms that are easily dispersible in cold water. For example. The amphiphilic protein portion anchors the pectin molecules to the oil phase. 1592 while the hydrophilic polysaccharide chains protrude into the aqueous phase thereby providing 1593 some steric repulsion. Nevertheless. and methyl hydroxypropyl cellulose (MHPC). but tend to become 1585 insoluble when the solution is heated above a critical temperature (around 50 – 90 ºC). salt and freeze-thaw cycling. SC Other polysaccharides: A number of other surface-active polysaccharides have been studied M AN U 1573 RI PT 1563 1574 for their potential use as emulsifiers in oil-in-water emulsions. e. 1993). which make it insoluble in water.. 2012. Although these polysaccharides 1575 are not widely used in the beverage industry at present they may find some applications in the 1576 future.

1609 1610 7.3. 2007). McClements. and 1618 will tend to flocculate at pH values close to their isoelectric points or when the ionic strength 1619 exceeds a certain level (Demetriades. 2002a. Yoshida. 1614 The interfacial coatings formed by proteins are usually relatively thin and electrically charged. 2010. 2008).2. protein-stabilized 1617 emulsions are particularly sensitive to pH and ionic strength effects (Figures 20 and 21).. Similar to 1599 gum Arabic and beet pectin. Yoshida. but the most 1613 widely used in the food industry are those derived from bovine milk: casein and whey proteins. & Corredig. globular AC C EP TE D 1608 . et al. Furuta. 1607 M AN U 1604 Research is continuing in this area. et al. and it is likely that a variety of other polysaccharidebased emulsifiers will be identified that may be suitable for stabilization of beverage emulsions. whereas less than 1% whey protein can be used 1623 (Chanamai & McClements. Protein-based emulsifiers Proteins are widely used in the food industry to stabilize various commercial food and 1611 beverage products. 1598 Maeda. et al. 2004.. 2004).. Maeda. but they are not commonly used to stabilize soft drinks. On the other hand. SC 1603 RI PT 1597 Corn fiber gum (CFG) is a by-product of the milling of corn (Yadav. as much as 20 % gum arabic may be required to 1622 produce a stable 12. and therefore they can also 1595 generate an electrostatic repulsion (Nakauma. The surface activity of this polysaccharide may 1606 also be due to the presence of small amounts of protein or lipids that are associated with it. et 1602 al. 1995b). For example. meat. Surface-active 1612 proteins can be isolated from various sources. Takahashi. 1596 Soy soluble polysaccharide (SSPS) is a soluble. including milk. fish. 2008). 1615 and hence the major mechanism preventing droplet flocculation in protein-stabilized emulsions 1616 is electrostatic repulsion (rather than steric repulsion).. 2007). Tse & Reineccius.5). & Hicks. 1997b. 2004). Hotchkiss. & Corredig.5 wt% oil-in-water emulsion. Preliminary studies have shown that CFG can facilitate the formation and stability 1605 of oil-in-water emulsions (Yadav. 1620 Proteins can typically be used at much lower levels that amphiphilic polysaccharides to 1621 stabilize oil-in-water emulsions. Nakamura. Dickinson. 1997a. Consequently. and plants.2. SSPS is believed to have a protein backbone that anchors the 1600 molecule to the oil phase and hydrophilic anionic polysaccharide chains that protrude into the 1601 aqueous phase and provide stabilization through steric and electrostatic repulsion (Nakauma. Johnston. acidic polysaccharide extracted from okara that has a molecular structure that closely resembles pectin (Nakamura.ACCEPTED MANUSCRIPT 55 1594 charge because of the presence of carboxylic groups (pKa = 3.

whey protein . Klein. & McClements. et al. These reactive groups increase the attractive 1650 interactions between droplets. SC 1633 RI PT 1624 A number of other methods have also been developed to improve the emulsifying properties of protein ingredients. and thermal 1625 processing than polysaccharide stabilized emulsions as shown in Figure 20 (Chanamai & 1626 McClements. and thermal 1627 processing can often be improved by mixing them with ionic polysaccharides either before or 1628 after homogenization. 2006. 2007. 2002a). because these proteins unfold when the temperature 1648 exceeds the thermal denaturation temperature thereby exposing reactive non-polar and sulfhydryl 1649 groups (Kim. The stability of protein-stabilized emulsions to pH. These ionic polysaccharides form an interfacial complex with the adsorbed protein 1631 molecules. 1637 M AN U 1634 Globular Proteins: Native globular proteins tend to have fairly compact spheroid structures with the non-polar amino acids contained within their hydrophobic interiors (away from water) 1639 and the polar amino acids located at the exterior (in contact with water). 2004). such as gum arabic. 2011). Harnsilawat. Globular proteins tend to form relatively thin interfacial coatings around fat droplets. pea. 2006. and blending of the proteins with 1636 other ingredients. Emulsions stabilized by globular proteins are also 1647 particularly sensitive to heat treatments. enzymatic or genetic means. alginate. They are therefore particularly sensitive to droplet flocculation at pH 1645 values near the isoelectric point (where the droplet charge is low) or at high salt concentrations 1646 (where the droplet charge is screened). physical.ACCEPTED MANUSCRIPT 56 protein stabilized emulsions are much more susceptible to pH. modification of protein 1635 structure by chemical. which increases the steric and electrostatic repulsion between the droplets 1632 (Dickinson. A number of different whey protein ingredients are available for use 1654 in the food industry as emulsifiers. & McClements. egg. soy.. pectin. Pongsawatmanit. ionic strength. although not all of these methods are legally permitted at present. and carrageenan (Guzey & 1629 McClements. including limited hydrolysis to form peptides. 2002). There are many sources 1640 of globular proteins in foods that are surface-active and capable of forming and stabilizing 1641 emulsions. 1642 2005b). including whey protein concentrate (WPC). 1630 2010). which may lead to droplet flocculation through increased 1651 hydrophobic attraction and disulfide bond formation. 1643 and therefore primarily stabilize emulsions against flocculation through electrostatic repulsion 1644 (McClements. salts. such as those from whey. Decker. and various other plants (McClements. AC C EP TE D 1638 1652 The most common source of globular proteins in the food industry is the whey protein 1653 derived from bovine milk.

but undergoes a coil-to- 1676 helix transition upon cooling below a critical temperature. 1674 The isoelectric point of Type A gelatin (∼7-9) tends be higher than that of Type B gelatin (∼5). 1683 and purified protein fractions. especially in the presence of salts that screen 1666 electrostatic interactions (Kim. it often produces 1679 relatively large droplet sizes when used in isolation. WPC and WPI are commonly used as emulsifiers in commercial food and beverage 1658 products. and caseins from bovine 1671 milk. and ≈ 5% serum albumin (McClements. The isoelectric point of the 1662 major whey proteins is around pH 5. and so they are prone to droplet 1665 aggregation when heated above this temperature. These molecules tend to have a more 1669 flexible random coil type structure (although they often retain some secondary structure). ≈ 24% α-lactalbumin.ACCEPTED MANUSCRIPT 57 isolate (WPI). Gelatin has been shown to be surface-active and 1678 capable of acting as an emulsifier in oil-in-water emulsions. and therefore droplets stabilized by whey proteins tend to 1663 flocculate around this pH. Gelatin is a relatively high molecular weight protein derived from fish. which is about 10 to 25 ºC for animal 1677 gelatin and about 0 to 5 ºC for fish gelatin. αS2 (∼ 11%). β (∼ 32%) and κ (∼ 11%). The 1670 main sources of flexible proteins are gelatin from fish and animals. SC M AN U 1667 RI PT 1655 Flexible Proteins: Another group of protein-based emulsifiers commonly used in foods can be classified as flexible proteins (Dickinson. There are four main protein fractions in 1684 casein: αS1 (∼ 44%). AC C EP TE D 1668 1681 There are various casein-based emulsifiers that can be purchased commercially with 1682 different compositions and functional properties. calcium caseinate. and especially between about pH 4 to 6 (Figure 20). ≈ 15% 1661 immunoglobulins. porcine. It is typically prepared by disrupting the native structure of 1673 collagen by boiling it in the presence of either acid (Type A gelatin) or base (Type B gelatin). such as a β-casein.3) close to the protein’s . 1656 These ingredients normally come as white powders that are dissolved in water prior to 1657 utilization. The thermal 1664 denaturation temperature of whey proteins is around 70 to 80 ºC.. 2005b).5 – 5. et al. 1992a). and therefore it may be utilized with other 1680 ingredients to improve its effectiveness at forming and stabilizing emulsions. 2005b). 2002). Nevertheless. whereas β-lactoglobulin and α-lactalbumin are more frequently used in fundamental 1659 studies of protein functionality in research laboratories. such as sodium caseinate. Casein-coated droplets have been 1685 shown to be unstable to droplet flocculation at pH values (3. Whey protein actually contains a 1660 mixture of globular proteins: ≈ 55% β-lactoglobulin. and highly purified protein fractions such as β-lactoglobulin and α-lactalbumin. 1675 Gelatin exists as a random coil molecule at relatively high temperatures. or bovine 1672 collagen (McClements.

1706 The nature of the fatty acid and polyoxyethylene chains determines the nomenclature and 1707 functional properties of the surfactant. However.3. In addition. Stauffer.2. A summary of some small-molecule 1703 surfactants that could be utilized in beverage emulsions is given in Table 4. small-molecule surfactants consist of a polar head-group and a non-polar tail 1691 group (Kralova & Sjoblom. anionic or cationic. Caseinate-stabilized emulsions tend to be more stable to heating than whey 1687 protein-stabilized emulsions. while the tail group may vary in the number. Tween 40 (monopalmitate). 1708 Tween 60 (monostearate). McClements. presumably because the relatively flexible casein molecules do not 1688 undergo appreciable heat-induced conformational changes like globular proteins do. Since Tweens are nonionic they tend 1711 to produce droplets that are stable to aggregation over a wide range of pH and ionic strength 1712 values. the food industry has been trying to 1700 replace synthetic small molecule surfactants with emulsifiers that are natural and more label 1701 friendly due to consumer demands. length. Recently. 1999). Despite these advantages.3. 2005b. 1714 1715 AC C EP 1705 Sugar esters: Sugar esters are synthetic nonionic surfactants that consist of a polar sugar esterified to a fatty acid chain. Surfactants are also able to stabilize emulsions at lower concentrations 1699 than amphiphilic biopolymers. and degree of 1693 unsaturation of the chains. 1689 1690 7. SC M AN U TE D 1704 RI PT 1686 Tweens: Tweens (also sold under the name polysorbates) are synthetic non-ionic surfactants that consist of a non-polar fatty acid group esterified to a polar polyoxyethylene sorbitan group. Tween-coated droplets may become unstable to coalescence at elevated 1713 temperatures close to the phase inversion temperature. many surfactants are able 1696 to form smaller oil droplets than amphiphilic biopolymers using high energy methods because 1697 they can adsorb more quickly to the oil-water interfaces during homogenization and lower the 1698 interfacial tension more. some natural small molecule surfactants have 1702 become commercially available. 2009.ACCEPTED MANUSCRIPT 58 isoelectric point.9 and 16). such as quillaja saponin. There has been growing interest in the utilization of sugar esters . They are therefore predominantly water-soluble. Tween 20 (monolaurate). The head group may be 1692 non-ionic. form micelles 1710 in aqueous solutions. and stabilize oil-in-water emulsions. Small-molecule Surfactants In general. Many surfactants can be used to fabricate beverage emulsions using 1694 either low or high energy approaches. and Tween 80 (monooleate) are hydrophilic molecules with relatively 1709 high HLB values (14. which is different from amphiphilic biopolymers that can 1695 only be used to fabricate them using high energy methods.

1742 Zomer. Garti. Emulsions formed using sucrose monopalmitate (SMP) as the only 1731 emulsifier are highly unstable to aggregation when stored at acidic pH values (pH 3. Otomo. which can be attributed to their desirable sensory attributes. Guely. microemulsions. 2004). 2013. 2013). Budai-Szucs. et al. which 1732 has been attributed to a reduction of droplet charge (Rao & McClements. which are high molecular weight glycosides consisting of a sugar 1743 moiety attached to a triterpene or a steroid aglycone (Hostettmann & Marston. fucose.. have high HLB numbers. and are therefore often 1720 perceived as being more label-friendly than petrochemical-based surfactants (Huck-Iriart. & Fanun. sugar esters 1719 are produced from natural products. galactose.g. The 1744 saponins are surface active substances because they contain both hydrophilic regions (such as 1745 rhamnose. Aserin. and can stabilize O/W emulsions 1725 (Garti. 1721 Candal. Glatter. which means they are 1724 relatively hydrophilic.ACCEPTED MANUSCRIPT 59 as emulsifiers within the food and beverage industry (Szuts. 1997. Clement. Aserin. Sher. & 1717 Szabó-Révész. 2000. 2011). such as sucrose and vegetable oil. Leser. Marchal. et al. These studies have shown that sucrose monoesters can form a range of different colloidal 1729 structures depending on system composition and temperature. It has been found to contain surface active components that are 1738 capable of forming surfactant micelles and stabilizing oil-in-water emulsions (Mitra & Dungan. water-soluble. and glucuronic acid) and hydrophobic regions 1746 (such as quillaic acid and gypsogenic acid) on the same molecule (Mitra & Dungan. Sidhu AC C EP 1736 . Waller & Yamasaki. arabinose. xylose. Kamerling. e. 1995). 2001). Sucrose 1723 monoesters have a single fatty acid attached to the sucrose molecule. Clement. low toxicity. 1996a. Fanun. ten Hove. 1733 emulsions that are stable across a wide range of pH can be produced by mixing SMP with a co- 1734 surfactant (such as lecithin) that increases the electrostatic repulsion between droplets at low pH 1735 (Choi. However. 2011). Eros. Yang. van de Werken.. van Setten. & McClements. 2010. 1739 1997. & Choplin. 2009). In addition.. 1730 nanoemulsions or emulsions. A number of researchers 1726 have previously examined the structure. 1999. & van de Werken. & Herrera. 2000.5). & Fanun. Leser. 2010). TE D M AN U SC RI PT 1716 Quillaja Saponin: Quillaja saponin is a natural surfactant extracted from the bark of the 1737 Quillaja saponaria Molina tree. Yang & 1740 McClements. Garti. 1998. & Leser. The major components within this extract have been reported to be saponins 1741 (van Setten. and functionality of sucrose monoesters 1727 (Fanun. 1995) . properties. Sucrose fatty acid esters are non-ionic surfactants that have a sucrose 1722 moiety as a hydrophilic head group and one or more fatty acids as lipophilic tail groups. Garti. Wiertz. & Kersten. et al. 1728 1999). 1996b. 1718 and high biodegradability (Sadtler..

2013. 1986). temperature. 2013). whereas 1766 polysaccharides tend to be better at producing emulsions that are more stable to environmental 1767 conditions than proteins. and may be formed 1773 either before or after homogenization (McClements 2004). 1749 et al. This ingredient 1752 was released in 2008 and has been marketed as a replacement for gum acacia in beverage 1753 emulsions. e. 2011. Guzey & McClements. ionic strength. Q-Naturale® can be used at a low level. ionic strength. According to the suppliers. It is also organic certified and is stable in products stored at ambient or 1756 cold temperatures for up to a year. pH. 1750 A food ingredient based on the quillaja saponin extract has recently been produced by the National Starch Company (Bridgewater. quillaja extract has also been used as a foam-stabilizing agent in beverages. freeze-thaw cycling (McClements 1768 2004). and is stable in some forms of alcoholic beverages.3.ACCEPTED MANUSCRIPT 60 1747 & Oakenfull.2. economically viable and show 1775 benefits over existing ingredients before they find widespread utilization in the food industry. Ingredients based on protein- 1774 polysaccharide interactions will have to be legally acceptable. and temperature (Yang. These 1772 complexes may be held together either by physical or covalent interactions. The ingredient also comes in a liquid form. It AC C EP TE D 1759 ..g. unlike most forms of gum acacia or 1755 modified food starch. NJ) under the trade name Q-Naturale®. A number of researchers have shown 1770 that protein-polysaccharide complexes may have better emulsifying properties than either of the 1771 biopolymers used in isolation (Dickinson. Mixed Emulsifier Systems There has been increasing interest in using mixed emulsifier systems with the aim of 1764 producing more label-friendly food ingredients. 2006). The beneficial attributes of these two kinds of biopolymer can be combined to produce 1769 small emulsion droplets with good environmental stability. The extract is added to the aqueous phase of a beverage to 1760 stabilize foam that forms at the neck of the beverage.. 2003. has high oil 1754 loading. Yang & McClements. Recent experiments have shown that it can be used to form emulsions 1748 containing small droplets that are stable to changes in pH. so that dissolution 1757 and hydration steps are unnecessary. This foam is considered a positive attribute 1761 in root beer and some citrus juices in various parts of the world. SC M AN U 1758 RI PT 1751 Aside from its use as a beverage emulsion emulsifier. 1762 1763 7. Proteins tend to be better at producing small 1765 emulsion droplets when used at low concentrations than polysaccharides.4.

2005a). i.2. The 1796 creaming rate can be reduced by decreasing the density contrast between the oil droplets and the 1797 surrounding aqueous phase (Equation 3). The stability of a beverage 1790 emulsion to gravitational separation can therefore be improved by ensuring that the density of the 1791 oil droplets is similar to that of the surrounding aqueous phase. such as lysolecithin. The densities of some of the 1792 major components found in beverage emulsions are listed in Table 3. 1794 Consequently. 1800 7.3.e. and the reciprocal 1788 of the aqueous phase viscosity (η0) (Equation 3). droplets containing these oils tend to move upward during storage leading to 1795 “ringing”. The densities of flavor 1793 oils and vegetable oils are considerably lower than those of water and aqueous sugar solutions. or dammar gum (Table 3). If ∆ρ is positive the particles move downwards 1789 (sediment). the creaming rate of a droplet within an emulsion is given by Stokes’ law 1786 (McClements.ACCEPTED MANUSCRIPT 61 1776 should be noted that gum arabic is actually a naturally occurring protein-polysaccharide complex 1777 that is already widely used in the food industry as an emulsifier. There are a number of different factors that will . but their stability can be greatly improved by 1780 combining them with co-surfactants. the density contrast between the two phases (∆ρ).. Mechanism of Action Weighting agents are additives incorporated into the oil phase of certain types of beverage SC 1783 RI PT 1778 emulsions to inhibit gravitational separation of the oil droplets (McClements. which are 1799 hydrophobic components that have a density that is considerably greater than water (Table 3). As mentioned earlier.1. SAIB (Sucrose acetate isobutyrate). As 1785 discussed earlier. The most common means of increasing the density of 1798 the oil phase so that it matches that of the aqueous phase is to add weighting agents. sucrose monoesters produce emulsions that are not very stable under 1779 acidic conditions when they are used in isolation. Factors Influencing Selection AC C EP TE D M AN U 1784 1801 A number of different weighting agents are available for utilization within commercial 1802 beverage products.3.3. This equation predicts that the rate of creaming is proportional to the 1787 droplet radius squared (r2). the formation of a visible ring of fat droplets at the surface of the product. 1803 ester gum. 2005b). such as brominated vegetable oil (BVO). but if ∆ρ is negative they move upwards (creaming). Weighting Agents 1782 7. 1781 7.

or polysaccharides) that 1820 have a higher density than both the oil and the water phases. 1824 2011). However. However. then the overall 1822 density of the emulsion droplet (oil core + interfacial layer) may become similar to that of the 1823 aqueous phase. phospholipids. whereas BVO and SAIB are synthetic ingredients. proteins. There are also 1829 differences in the “label-friendliness” of different weighting agents. The amount of 1808 a weighting agent that is required to match the density of the oil and aqueous phases depends on 1809 its density: the higher the density. Sugars increase the aqueous phase density 1813 and would therefore be expected to increase the density contrast between the oil and aqueous 1814 phases. The interfacial layer is usually 1819 made up of emulsifiers (such as surfactants. sugars also increase the viscosity of the 1815 continuous phase. which will influence the preparation of the oil phase 1811 and the formation of stable emulsions by homogenization. and so the adsorbed emulsifier acts as a weighting agent itself (McClements. so that the creaming rate in 1816 sugar solutions is not much greater than in pure water (Chanamai & McClements. which alters their ease of use and functional properties. Physicochemical factors: The bulk physicochemical properties of commercial weighting 1807 agents vary considerably. the overall density of an emulsion droplet actually depends on the density and volume of the oil phase and the interfacial layer. Weighting agents also vary in 1810 their rheological and solubility properties. the smaller the amount needed. This low concentration of allowable . respectively. many countries have restricted the amount of weighting 1833 agents that can be found in the final product. Many beverage emulsions are 1812 sweetened by adding sugars to the aqueous phase. EP 1825 TE D 1818 Legal and Labeling Factors: There are legal limits on the amount of each type of weighting agent that can be used in beverages.ACCEPTED MANUSCRIPT 62 1804 determine which of these different components is suitable for application within a specific 1805 beverage product. AC C 1826 1831 Brominated vegetable oil (BVO) and ester gum are the two most commonly used weighting 1832 agents in beverage emulsions. the United States restricts BVO and 1834 ester gum’s use to 15 and 100 ppm per serving. 1827 These legal limits vary from country to country and therefore a manufacturer must be aware of 1828 the appropriate legislation in each country the product will be marketed in. which should accelerate creaming. These two effects largely cancel each other out. which must be adhered to when formulating a project. 2000). When the thickness of the 1821 interfacial layer is appreciable compared to the dimensions of the oil core. Dammar and ester gum can 1830 be considered to be natural ingredients. For example. SC M AN U 1817 RI PT 1806 As mentioned previously.

Beverage 1836 emulsions are one of the few products where these weighting agents can be used to reduce the 1837 creaming rate. USA). It is also possible to blend two or 1838 more types of weighting agents together to achieve density matching but remain below their 1839 individual restriction levels. or olive oil.2. et 1863 al.3. and a permitted usage level of 15 ppm per serving in the United 1845 States. Ester Gum Ester gum is a hydrophobic polymer made when glycerol is esterified to gum rosin 1853 harvested from trees (such as pine trees). 2000). which has led some major beverage manufacturers to replace it with more natural 1847 alternatives. 2011). because the oil phase content is so low (<0. In 2013. Nevertheless. Brominated Vegetable Oil Brominated vegetable oil (BVO) is made when bromine is added to the double bonds of the 1843 triacylglycerol molecules in corn.1. cotton seed. AC C EP TE D M AN U SC RI PT 1835 . Ester gum may not be considered to be a natural food ingredient 1855 due to the esterification step used in its preparation. Nevertheless. it acts like a ripening inhibitor (Lim. 1851 1852 7. soybean. It typically has a density 1844 between 1240 and 1330 kg m- 1840 7. It 1859 performs similarly to BVO but a greater concentration of ester gum has to be added to the oil 1860 phase in order to raise the density (Chanamai & McClements.. it is derived from natural 1856 components (gum rosin) and non-animal glycerol. Ingredient Examples 1841 1842 7. It is normally supplied as a crystalline solid that can be 1854 incorporated into the oil phase.e.. i.3.. there has recently been consumer concern about the presence of BVO in 1846 soft drinks.1%). Even though BVO is permitted 1849 for use in the United States. a leading beverage manufacturer removed BVO from a major product line 1848 after receiving consumer complaints and petitions against its use. it has been banned from use in beverages in the European Union and 1850 Asia. Ester gum has a density of around 1080 1858 kg m-3 and a permitted usage level of 100 ppm per serving in the United States (FDA. This behavior would probably be demonstrated by all weighting agents because they 1864 are highly hydrophobic materials with low water-solubilities.ACCEPTED MANUSCRIPT 63 weighting agents restricts the type of products that BVO and ester gum can be used in. and the name “ester gum” may appear to be 1857 more label friendly to consumers than BVO or SAIB. recent studies have shown that ester gum also retards droplet growth in 1862 model flavor emulsions through Ostwald ripening. Aside from its traditional 1861 use as a weighting agent.3.

1992). a major form of physical instability in many beverage emulsions is TE D 1880 RI PT 1865 1866 Ostwald ripening. 1892 AC C EP 1881 An effective means of inhibiting or preventing Ostwald ripening in an emulsion is to add a 1893 hydrophobic component with a very low water-solubility to the oil phase prior to 1894 homogenization (Kabalnov.3.454. 1992). SAIB is usually supplied in the 1868 form of a high viscosity transparent liquid that can be mixed with the oil phase prior to 1869 homogenization. and therefore 1890 cloud emulsions prepared from these types of oil are not prone to Ostwald ripening (Coupland. triacylglycerol oils (such as corn. 2001.4.3. On the other hand.4. & Shchukin. This hydrophobic compound is . 1996).3. Pertzov. 1879 7. USA). 1873 1874 7. the increase in mean droplet 1884 diameter over time can be described by Equation 6 given earlier (Kabalnov & Shchukin. 1987). The level of SAIB in beverages is currently restricted to 300 ppm per serving in the 1872 United States (FDA. 1885 This equation predicts that the Ostwald ripening rate increases as the solubility of the oil phase in 1886 the aqueous phase increases. SAIB also has good stability to chemical degradation due to lipid 1871 oxidation. Dammar Gum Dammar gum is a natural weighting agent that is isolated from an exudate of 1875 Caesalpinaceae and Dipterocarpaceae shrubs. Dammar gum is approved 1877 for use in several countries. & McClements.3. sunflower.ACCEPTED MANUSCRIPT 64 7. Many flavor oils have a relatively high water-solubility and are 1887 therefore particularly prone to droplet growth through this mechanism (Rao & McClements. Ripening Inhibitors SC M AN U As discussed previously. and a 1870 density of ≈ 1146 kg m-3. Of the four weighting agents mentioned in this 1876 review. dammar gum has the lowest density at 1060 kg m-3 (Table 3). or canola oils) contain 1889 large non-polar triacylglycerol molecules with relatively low water-solubilities. but it is not currently approved for use in the USA and it so does not 1878 have GRAS status. a refractive index of ≈ 1. Sucrose Acetate Isobutyrate Sucrose acetate isobutyrate (SAIB) is a synthetic weighting agent produced by the 1867 esterification of sucrose with acetic and isobutyric anhydrides. which is the process whereby the mean droplet size grows during storage due 1882 to diffusion of oil molecules from small droplets to large droplets (Kabalnov. 1888 2012b). Once steady state conditions have been achieved.3. Kabalnov & 1883 Shchukin. 1891 Weiss. It has a molecular weight of ≈ 845 g mol-1. Lovy.

Thickening agents are usually hydrophilic biopolymers that dissolve in the aqueous 1910 phase and occupy a volume that is much larger than the volume of the polymer chain itself 1911 (McClements. 2011).5.g.. Thus. 1× and 3×) (Rao & McClements.3..g. Mechanism of Action M AN U 1907 SC 1900 Thickening agents are ingredients that are added to beverage emulsions to increase the viscosity of the aqueous phase.ACCEPTED MANUSCRIPT 65 referred to as a “ripening inhibitor” due to its ability to slow droplet growth through this 1896 mechanism (Lim. molecular weight.. 1903 which may account for the better stability of high-fold lemon oils (e. Thickening Agents 1906 7. Typically. and therefore retard droplet creaming and alter product 1909 mouthfeel. 2012c).. Rv increases as the molar mass. et al.1.1. et al.. xanthan gum is a 1924 particularly effective thickening agent because it has a high molecular weight and is highly .. which is discussed in more detail in Section 5. 1923 extension. 2005b). 2011.g.. 1899 RI PT 1895 Recent studies have shown that Ostwald ripening may be inhibited in flavor oil emulsions by adding long chain triglycerides (such as corn oil) (McClements.5. It has also been proposed that some of 1902 the water-insoluble components within flavor oils themselves may act as ripening inhibitors. 1987). the more effective is the 1922 polymer at increasing the viscosity of a solution. 1913 conformation.5 Rvφ) (9) AC C 1915 TE D 1908 where φ is the volume fraction of the biopolymer chain. 2012). The effectiveness of a thickening agent at increasing the viscosity of an 1912 aqueous solution is largely determined by its molecular characteristics (e. and Rv is the volume ratio (Rv = 1919 Vsphere / Vpolymer).. 2012) or by adding 1901 weighting agents (such as ester gum) (Lim. 1905 7. et al. The ability of low water-solubility 1897 compounds to retard Ostwald ripening in emulsions can be attributed to an entropy of mixing 1898 effect (Kabalnov. where Vsphere is the effective volume that the biopolymer occupies in solution 1920 (which includes the polymer chain and any trapped solvent). et al. and Vpolymer is the volume occupied 1921 by the polymer chain itself. et al. 10×) to Ostwald ripening 1904 than low-fold lemon oils (e. and self-association of biopolymer molecules increases. McClements. To a first approximation the viscosity of a dilute aqueous 1914 solution containing a hydrophilic biopolymer can be described by Einstein’s equation: 1917 1918 EP 1916 η = η0 (1 + 2. The higher the value of the volume ratio. and interactions).

5). Proteins are positive below their 1950 isoelectric point. since electrostatic interactions 1941 influence ingredient interactions. carboxyl groups (e.g.ACCEPTED MANUSCRIPT 66 extended in aqueous solutions and therefore has a large Rv value. such as helix-coil 1937 transition temperatures (for carrageenan. hydrophobicity.g. xanthan. electrical properties (charge groups 1938 and pKa values). It should be noted that thickening agents can actually promote emulsion 1928 instability under certain conditions. 1944 cellulose.g. some are anionic (e.g. alginate. Some biopolymers are neutral (e. and mouthfeel. It is important to establish the solution and environmental 1935 conditions under which the thickening agent must function. ion sensitivity.(pKa ≈ 3.g. pectin. -NH3+ ↔ . and negative above it (Figure 20). some are cationic (e.. carrageenan). Bridging flocculation can occur when polymer molecules are attracted to the 1930 surfaces of oil droplets. alginate. whereas depletion flocculation occurs when they polymer molecules are 1931 dispersed in the continuous phase and their concentration exceeds a particular value.5.5). gelatin). LBG). locust bean gum. whereas cationic polysaccharides tend to be neutral at pH values 1949 sufficiently above their pKa value but positive below.. starch.NH2 (pKa ≈ 6.g. 1932 7. 1997).g... 1940 of the biopolymer molecules used (ζ-potential versus pH profile). The electrical charge on 1942 biopolymers depends on the nature of any ionic groups along the chain background. alginate. and chemical/enzymatic stability (Whistler & 1939 BeMiller. 1952 pectin. Anionic polysaccharides tend to be neutral at pH values sufficiently below their pKa 1948 value but negative above. M AN U 1933 AC C EP TE D For some applications. it is important to establish the electrical characteristics .2. This usually requires knowledge of 1936 the physicochemical properties of the biopolymer molecules involved. due to their ability to induce bridging or depletion 1929 flocculation. carboxymethylcellulose) and amino groups (e.(pKa ≈ 2). The most common 1954 charged groups on proteins are carboxyl and amino groups. Factors Influencing Selection SC RI PT 1925 There are a number of factors that must be considered when selecting a suitable thickening 1934 agent for use in beverage emulsions.. 1927 or carrageenan. emulsion stability. 1945 chitosan and polylysine). -CO2H ↔ -CO2. Most thickening agents used in 1926 beverages are long-chain hydrophilic polysaccharides. xanthan). The most common charged groups on 1951 polysaccharide thickening agents are sulfate groups (e. The magnitude of the 1946 electrical charge on ionic biopolymers depends on the pH relative to the pKa value of the ionic 1947 groups.. and some are amphoteric (e. as well as 1943 solution conditions (pH and ionic composition). such as xanthan. carrageenan. pectin). chitosan): -SO4H ↔ - 1953 SO4..

Conventionally. It has been proposed that mammals 1978 evolved to perceive a pleasant sensation after ingestion of sugar-rich foods because these foods 1979 are a ready source of energy in nature (e. and functional properties of 1972 thickening agents in foods and beverages (Cui. Ingredient Examples M AN U SC RI PT 1955 There are many different types of thickening agents that can be used in commercial 1967 beverage products.1 Mechanism of Action EP 1975 TE D 1966 Beverage emulsions are sweetened by adding artificial or natural substances that interact with specific taste receptors on the tongue to provide the perception of sweetness (Fernstrom. A wide variety of substances 1980 have molecular structures that can induce a sweet sensation. 2009). degrees of branching. McCaughey.5. 2012. conformations. or calcium 1958 may bind to oppositely charged groups on biopolymer chains. and transition temperatures. 2008. potassium. pectin can start to depolymerize when exposed to neutral or alkaline 1962 conditions as a result of a base-catalyzed β-elimination reaction that breaks down its sugar chain. In addition. 1964 2009).6. 2010. Meyers & Brewer. physicochemical. A summary of thickening agents that could 1970 be utilized in beverage emulsions is given in Table 5. Imeson. this breakdown can result in a decline in viscosity and loss of texture (Sila et al. 1963 Over time. which alters how they react with the 1983 sweetness receptors in the mouth.. fruits and berries).. 1957 and other biopolymers. 1965 7.6. Phillips & Williams. Monovalent or multivalent ions such as sodium.3. et 1977 al. These thickening agents differ in their chemical compositions. which 1969 causes variations in their functional performances. Sweeteners 1974 7. surfactants. such as mineral ions. altering their overall charge 1959 characteristics. although they vary greatly in the 1981 concentrations required to produce sweetness. molecular 1968 weight distributions. For example. 1973 7.. the sweetness of substances is compared to AC C 1976 .g. There are a number of excellent books that 1971 provide detailed information about the molecular. Sugar molecules have different sweetness 1982 intensities due to differences in their molecular structures. 2005. 2008). knowledge of the type of environmental and solution conditions 1960 present within a particular food is often important for selecting the most appropriate thickening 1961 agent.ACCEPTED MANUSCRIPT 67 The electrical characteristics of thickening agents in aqueous solutions may also be altered 1956 by interactions with other ionic species in their environment.


that of sucrose (table sugar) which is taken to have a Sweetness of 100. The relative sweetness


of different types of sweetener is established using carefully controlled sensory tests. Fructose is


the sweetest of all common sugars because it has just the right dimensions and bond orientations


to strongly interact with the sweetness receptors in the mouth. However, many natural and


artificial compounds have much strong sweetness intensities than sucrose, and therefore can be


used at much lower levels, which is the basis of many high-intensity sweeteners used in low-


calorie products.


7.6.2 Factors Influencing Selection





A number of factors must be considered when selecting a suitable sweetening system for a
commercial beverage product. The sweeteners used must provide a flavor profile that consumers


find acceptable and desirable. One of the main limitations of many high-intensity sweeteners is


that they do not produce a flavor profile similar to that normally provided by sugars (Nahon,


Roozen, & DeGraaf, 1996), or that they produce undesirable off-flavors (such as bitterness or


metallic) or mouthfeel (such as astringency) (DuBois & Prakash, 2012). In addition, the


sweeteners must remain physically and chemically stable within the product throughout


processing, transport, and storage. Some sweeteners may breakdown when exposed to elevated


temperatures and are therefore unsuitable for use in beverages that undergo thermal processing.


Concern about overweight and obesity has driven consumer demand for reduced calorie


products, which has led the beverage industry to produce low- and mid-calorie versions of their


conventional high-calorie products. However, many of the high-intensity sweeteners used to


replace sugars have undesirable flavor profiles or are perceived as being “unnatural”, and so the


beverage industry is trying to introduce natural low-intensity sweeteners with desirable flavor


profiles (such as Stevia).


7.6.3. Ingredient Examples







There are many different types of sweeteners that can be used in commercial beverage


products, which vary according to their chemical structure, origins (natural versus artificial), and


intensity (low- versus high-intensity). The most commonly used low-intensity sweeteners are


sugars (such as sucrose, glucose, and fructose) and sugar alcohols (such as sorbitol, mannitol,


xylitol and erythritol). These substances may be added as individual ingredients, or they may be


part of more complex ingredients, such as high fructose corn syrup, honey, and sugar cane. The


human body does not have the appropriate enzymes in its digestive tract to break down sugar


alcohols in the same manner that sugars are broken down. Consequently, the body breaks sugar


alcohols down more slowly and less efficiently that sugars, which means they have less calories


per gram (about 50-75%), which may be useful for the development of reduced calorie products.


However, high-intensity sweeteners are more commonly used to produce low-calorie or medium-


calorie beverages, which may be artificial (such as Cyclamate, Aspartame, Acesulfame K,


Saccharin, Sucrolose, and Neotame) or natural (such as Stevia).


8. Commercial Aspects of Beverage Emulsion Formulation





Beverage emulsions are developed internally and externally by commercial manufacturers
of soft drinks products. External development is usually contracted to flavor houses that often


compete with each another for a flavor contract with a beverage manufacturer. This contract can


be worth thousands to millions of dollars depending on the product and length of the contract.


Factors considered for selecting the most appropriate flavor delivery system include stability,


cost, volume capacity, safety audits, kosher/halal certification, and the ingredient line of the


beverage emulsion. Because of these various factors, the best-tasting, most stable flavor may not


always be chosen as the final flavor used in a commercial application.





Beverage manufacturers normally supply flavor houses with a base of the intended product
into which the flavor is intended to be incorporated. A base consists of all ingredient components


except the flavor. By doing this, the manufacturers do not have to disclose confidential


formulations and the flavor houses can develop a flavor specific to the product. Shelf-life studies


(accelerated and non-accelerated) are performed to determine how well the prototype flavors


hold up in the formulation. If chemical or physical instabilities are observed, the flavor can be


reformulated to increase its stability. Depending on the project’s timeline this can take as little as


a few days or up to a year. If the product is being rushed to market and only a few days are


allotted for formulation, the flavor house can rely on past knowledge of how flavors behave in


similar products. This can enable the fast development of a flavor that will have a high-


probability of success in a given formulation. If development is done internally, the same steps


are followed: prototype formulation; shelf-life studies; reformulation (if necessary); and then








9. Recent Developments in Beverage Emulsions
There have been a number of recent developments and innovations in the beverage industry


over the past few years. In this section, we highlight a number of the most important ones. The


compositions and calorie content of a number of common commercial beverages is summarized


in Table 6, whereas some of the claims that can be made on beverages in given in Table 7.


9.1. “All-natural” Products and Cleaner Ingredient Lines



Consumers’ preference for natural products over artificial have caused manufacturers to


claim their products as “Natural” whenever possible. As attractive as a “Natural” claim is, it


comes at a product functionality and financial cost. In most cases, natural ingredients are more


expensive than synthetic and their functional properties are often not as robust. The use of


synthetic ingredients creates a cheaper, more stable product, but also one less attractive to many


consumers. A 2007 study by the University of Southampton (UK) linked synthetic colors and


additives to heightened hyperactivity in children (McCann, et al., 2007). This report led to a


consumer outcry for the removal of synthetic ingredients from food and beverage products aimed


at children, promoting many large companies to begin removing synthetic additives and colors.


One problem with replacing artificial additives with natural ones is that they are often much less


stable within commercial products. For example, natural colors may rapidly degrade in the


presence of acid, light, and heat. Consequently, many commercial products have had to be


reformulated to include effective strategies to extend their shelf-life, e.g., using antioxidants and


other preservatives to slow color fading.







The use of synthetic ingredients not only impacts consumer acceptance, but also limits retail
channels a product can compete within. Certain local and national grocery chains prohibit


artificial sweeteners, preservatives, and flavors in the foods they sell. The incorporation of


brominated vegetable oil (BVO), sucrose-acetate isobutyrate (SAIB), Tweens (polysorbate) or


modified-food starch into a product can restrict product sales in these marketplaces. Thus


beverage suppliers have to use alternative weighting agents (such as dammar gum or ester gum)


or emulsifiers (such as gum Arabic) in these products.




The removal of all synthetic components of a product may be unachievable for functional


and financial reasons. However, manufacturers can remove as many synthetic components as


possible to make “No, No, No” claims. For instance, an unnatural product can still claim “No

They usually contain a blend of ingredients. A “No. but it may be seen favorably by consumers. preservatives. These drinks may be taken before. but there have been renewed attempts to introduce 2088 them again recently in response to consumer desire for reduced calorie intake. energy drinks come as a 2095 Ready-to-Drink beverage (serving ~ 8 fluid ounces). these kinds of products have not sold well in the marketplace (with a number of 2087 products from different companies failing). No” claim is not as strong 2074 as a “Natural” claim. nutrients. proteins. and sweeteners”. 2086 Historically. or nutrients. minerals. AC C EP 2090 . 2098 Emulsion technology may be used in these products to deliver oil-soluble flavors. Recently. preservatives. clouding 2099 agents. there has been concern about 2101 the potential risks to certain individuals associated with consuming the large amounts of caffeine 2102 in some of these products. while still maintaining a desirable flavor profile. 2077 9. or Liquid Concentrate (dilute beverage serving ~ 8 fluid ounces).. flavors. These drinks contain blends of caloric (e. and Sucralose) to reduce the total calories in sweetened beverage products (typically by 2085 over a half compared to regular products). Further scientific research is required to demonstrate the 2100 claimed biological activity of many of these products.. Sucrose or High- 2083 Fructose Corn Syrup) and high-potency sweeteners (e. No. Acesulfame-Potassium. vitamins and/or stimulants (such as caffeine) that are proposed 2094 to replenish the bodies’ reserves and enhance performance. sugars. 2092 during. Typically. Low-Calorie and Mid-Calorie Soft Drinks 2078 RI PT 2073 Consumer perceptions about the potential link between overconsumption of sugary drinks and obesity promoted beverage manufacturers to create a variety of low or zero-calorie products 2080 (Slavin. 2089 9.ACCEPTED MANUSCRIPT 71 artificial colors.g. Ready-to-Drink shot (serving ~ 2 fluid 2096 ounces). Claims on product packaging 2075 are regulated by the US Food and Drug Administration within the Code of Federal Regulations 2076 (CFR). All the major 2097 commercial beverage manufacturers have products in this rapidly growing product category. and stimulants. 2084 Rebiana. or after some proposed activity.3. These products have been on the market for numerous years. but many 2081 consumers do not like their taste. 2012). Aspartame. specifically Title 21. Energy Drinks TE D M AN U SC 2079 Energy drinks are marketed as products that can enhance physical or mental activity by 2091 providing a rapid source of energy. and so the beverage industry has responded by developing a 2082 number of mid-calorie soft drinks. such as 2093 water.g.2.

flavor. 2120 9.5. charge.4. Minerals.ACCEPTED MANUSCRIPT 72 2103 9. More recently. Fortification with Vitamins. or give a slimy mouthfeel. sweetener. and nutrients that form a drinkable 2107 beverage upon dilution. Multivalent 2127 mineral ions (such as calcium) may precipitate from solution. such as physical state. promote precipitation of other 2128 components (such as proteins). This process 2109 still occurs within automated soda fountains found in many fast-food restaurants. minerals. such as vitamins. interactions. Beverage concentrates have been used since the nineteenth century 2108 when soda syrups were diluted by pharmacists prior to consumption by consumers. One recent successful product based on this principle involves squirting a small 2113 amount of the concentrate from a plastic bottle into a glass of water to form a zero-calorie 2114 beverage. solubility. and flavor profiles. Beverage Concentrates Beverage concentrates are products that are sold in a concentrated form that consumers then 2105 dilute with water prior to consumption. high acid. Concentrates may be in either a fluid or powdered form 2106 and contain ingredients such as sugars. dietary fibers. there is a push to fortify many beverage products with ingredients that 2122 are perceived as giving added health benefits. flavors. antioxidants. beverages have been developed that contain 2111 high-intensity sweeteners rather than sugars. and ω-3 fatty acids. 2118 buffer. For example. This segment of the beverage industry is growing rapidly AC C EP 2121 . 2130 each beverage product must be carefully formulated to take into account the specific types of 2131 nutraceutical components it contains. 2123 proteins. promote depletion flocculation. These nutraceutical additives vary greatly in their 2124 molecular. peptides. or cause undesirable mouthfeel. Consequently. and within 2110 some home soda beverage makers. which enable higher concentration factors to be 2112 attained. Dietary fibers may increase the 2129 viscosity of a product. and Nutraceuticals TE D 2116 As discussed earlier. M AN U SC RI PT 2104 Beverage concentrates have some unique developmental issues due to the fact that the 2117 ingredients are present in a highly concentrated form. and biological properties. A number of beverage manufacturers have launched products within this category in 2115 recent years. 2125 polarity. nutraceuticals and/or color concentrations can lead to accelerated chemical degradation 2119 reactions and shorter shelf lives. colors. carotenoids and polyunsaturated lipids 2126 may oxidize during storage and produce undesirable flavors or changes in color. For example. physicochemical.

patent expiration can also drive significant revenue loss once competitors have open 2154 access to the once-patented concept. and 2152 a manufacturer can gain additional revenue through lawsuits due to patent infringement. A patented product can be the main driver of strong revenue growth for years. but it was only in the 2000’s that it became a desired component of food 2159 products in the United States. whereas flavored and fruit-flavored waters are 2138 flavored with flavorants and fruit extracts. On the 2153 other hand. Predicting future trends and having the first product to market can give 2146 manufacturers a huge advantage against competitors. Enhanced water is fortified with 2137 electrolytes. Suspending grains in beverage products has been carried out in 2160 South America and Europe for many years. and fruit-flavored waters. Studying trends in other parts of the world and then modifying them to fit the intended 2157 marketplace can also be used to drive innovation. vitamins and other nutraceuticals. 2149 TE D 2145 One objective of new product innovation is to develop a product that is so novel that it can be patented. Acai Berry has been consumed in 2158 Brazil for decades. For instance. However. However. Reasons for rejection may 2148 include product unfamiliarity or a lack of consumer need for the product. respectively. flavored. . The federal government then grants the manufacturer a 20-year monopoly on that 2151 product type. Utilization of conventional emulsions in 2139 bottled waters to deliver oil-soluble flavors and nutraceuticals is limited because of the increase 2140 in turbidity caused by light scattering from the oil droplets. RI PT 2135 including enhanced. 2143 9. 2134 9. microemulsions and 2141 nanoemulsions that contain very fine droplets that do not scatter light strongly may be used for 2142 this purpose.ACCEPTED MANUSCRIPT 73 2132 with consumer demand for products that are perceived to be more beneficial to human health and 2133 wellness. being first to market is also a risk 2147 due to the possibility of a new product being rejected by consumers. but has only recently found its way into North 2161 America.6 Bottled Water There has been an appreciable increase in the global sales of bottled waters in recent years.7. AC C EP 2150 2155 New product innovation does not necessarily mean creating the first prototype of a new 2156 product. New Product Innovation M AN U 2144 SC 2136 New product innovation drives business growth and enables manufacturers to meet current consumer needs.

2187 A thorough understanding of the science and technology underlying the formation. or the 2172 replacement of expensive ingredients with inexpensive alternatives. 2188 and stability of beverage emulsions facilitates the development of innovative products. and fibers. salt. which can cause changes in the properties and stability 2179 of finished products. to remove ingredients that consumers perceive as being undesirable. 2173 10. properties. AC C EP TE D 2175 . to fortify beverages with ingredients that 2186 consumers perceive as desirable. Fusing elements from two different product 2166 categories is another way to innovate. consisting of small oil droplets dispersed within an aqueous 2176 medium. Such demands include the removal of ingredients from current products that 2170 consumers perceive as undesirable (such as artificial dyes or High-Fructose Corn Syrup). Nevertheless. nutraceuticals. the 2171 addition of desirable components (such as antioxidants. minerals. or nutraceutical lipids). but is not a widely used 2165 functional ingredient in foods and beverages. 2185 and artificial colors.ACCEPTED MANUSCRIPT 74 Determining a secondary use of manufacturing byproducts can also generate revenue 2163 through the development of functional food ingredients from material once destined for waste. RI PT 2162 New product development is an integral part of the food industry and changing out 2168 components of a beverage to meet current demands is a struggle that manufacturers have to 2169 consider every day. whey protein was once a byproduct of cheese production. and 2181 that they also ensure that ingredient quality and manufacturing conditions are standardized and 2182 monitored. The beverage industry must also reformulate products to meet changing market and 2183 consumer demands: to increase profits by replacing expensive ingredients with less expensive 2184 ones. or preservatives. there are still many challenges associated with developing successful 2177 commercial products. such as vitamins. To minimize any undesirable changes in product quality it is important that 2180 beverage manufacturers develop a robust initial formulation and manufacturing operation. and 2189 allows any production problems to be solved more rapidly. flavors. such as sugar. Conclusions M AN U 2174 SC 2167 In principle. minerals. 2164 For example. beverage emulsions are one of the simplest forms of oil-in-water emulsions used within the food industry. proteins. This review article has attempted to 2190 provide a comprehensive overview of the scientific and technological principles underlying 2191 beverage emulsion development. Beverage emulsions are prepared from various ingredients and processing 2178 operations that may vary from run-to-run.

Beneficial effects and oxidative stability of omega-3 long-chain polyunsaturated fatty acids. Design and production of nanoparticles formulated from nano-emulsion templates . 2201 12. Acknowledgments DJM would like to thank Prof. (2009). P. M.. Emulsification by ultrasound: drop size distribution and stability. L. AC C EP TE D M AN U SC RI PT 2194 . Latin American Applied Research. A.. E. Critical Reviews in Food Science and Nutrition. Anton. A. for 2195 which I am very grateful. NRI Grant and NSF-EPA-USDA Grant) and the 2200 Massachusetts Department of Agricultural Resources. Bioavailability of nanoparticles in nutrient and nutraceutical delivery. P. and Peter Given. J. (2005).. & Imrhan. Benoit. D. T. Trends in Food Science & Technology. Anton. Delmas. E. C. J.. Weiss.. & Decker. Gayet. (2008). Gaiani. J. E. Imran. 57(7). M. Double emulsions stabilized with hybrids of natural polymers for entrapment and slow release of active matters. Yuan Fang. Current Opinion in Colloid & Interface Science. (2009). H.. & Decker.. 14(1). 128(3).. Jacquot. International Journal of Pharmaceutics. Journal of Controlled Release. J. Eric Decker.. 108-109.ACCEPTED MANUSCRIPT 75 2192 2193 11. Weiss. & Garti. N. Boon. & Saulnier. Arab-Tehrany. J. 50(6).. Anil Gaonkar. 15-22.. 35(1). Basu. Deiber. Advances in Colloid and Interface Science. 515-532. including 2197 Ratjika Chanamai. A. M. 185-199. 6(1-2). Factors Influencing the Chemical Stability of Carotenoids in Foods. (2004). McClements. Wilhelm. We would also like 2198 to acknowledge that this material is partly based upon work supported by grants from the United 2199 States Department of Agriculture (CREES. Eric Dickinson for introducing him to the area of food biopolymers and colloids – it has led to many years of interesting and stimulating work. Acosta. 75-83. & Saulnier. J. Canselier.. (2007). D. A. P. 344(1-2).. N. E. McClements. The universality of low-energy nano-emulsification. F. B. Ultrasonics Sonochemistry. S. & Quemada. Role of Iron and Hydroperoxides in the Degradation of Lycopene in Oil-in-Water Emulsions. P. A.. International Journal of Pharmaceutics. & Gourdon. J. References 2202 2203 2204 2205 2206 2207 2208 2209 2210 2211 2212 2213 2214 2215 2216 2217 2218 2219 2220 2221 2222 2223 2224 2225 2226 2227 2228 2229 2230 Abismail. Aserin. (2009). N. We would also like to thank a number of colleagues in industry and 2196 academia who have provided valuable comments and suggestions on the manuscript. Berli. 61(3). Tomatoes versus lycopene in oxidative stress and carcinogenesis: conclusions from clinical trials. P... C. 24-33. A... (1999). C. (2010). 3-15. European Journal of Clinical Nutrition. N. Boon. (2007). A. C. & Vandamme. Benichou.. 2993-2998. J. 25(1). C. 29-41. P. V. 295-303. Nano-emulsions and nanocapsules by the PIT method: An investigation on the role of the temperature cycling on the emulsion phase inversion.A review. & Linder. Desobry. Anton. A. S... Journal of Agricultural and Food Chemistry. D... M. 142-147.. S.. On the viscosity of concentrated suspensions of charged colloids. 377(1-2).. (2012). 44-52. Benoit.

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Figure 1: Schematic representation of different kinds of colloidal dispersions that can be used in the beverage
industry: emulsions, nanoemulsions, and microemulsions.


• Thermodynamically unstable
• d > 100 nm
• Optically opaque




• Thermodynamically unstable
• d < 100 nm
• Transparent or slightly





• Thermodynamically stable
• d < 100 nm
• Transparent or slightly

sedimentation. coalescence.ACCEPTED MANUSCRIPT SC Kinetically Stable Nanoemulsion RI PT Figure 2: Schematic diagram of most common instability mechanisms that occur in food emulsions: creaming. flocculation. TE D M AN U Gravitational Separation AC C EP Sedimentation Creaming Flocculation Coalescence or Ostwald Ripening Oiling Off . Ostwald ripening and phase inversion.

ACCEPTED MANUSCRIPT SC RI PT Figure 3. TE D AC C Charge - + + + - - - + - - + - EP Composition Interfacial properties Negative Neutral + + Particle Size M AN U Droplet Positive . such as size. composition. The particles in beverage emulsions can be designed to have different functional performances by varying their physicochemical and structural properties. charge and interfacial properties.

weakly flocculated.ACCEPTED MANUSCRIPT w(h) RI PT Energy Barrier h Attraction AC C EP TE D M AN U SC Repulsion Coalesced 1º Min 2º Min Figure 4. Schematic representation of the interaction potential between two emulsion droplets. strongly flocculated. The droplets may be stable. or coalesced depending on the attractive and repulsive forces between them. .

AC C EP TE D M AN U SC RI PT ACCEPTED MANUSCRIPT Figure 5. Lipid droplets have a major impact on the texture. appearance and stability of emulsions .

Initial flavor intensity of emulsions with fixed flavor content is strongly dependent on oil droplet content. .M AN U SC RI PT ACCEPTED MANUSCRIPT AC C EP TE D Flavor Polarity Figure 6.

Droplet growth due to Ostwald ripening of orange oil emulsions can be inhibited by adding a corn oil. which acts as a ripening inhibitor (McClements et al 2012) .AC C EP TE D M AN U SC RI PT ACCEPTED MANUSCRIPT Figure 7.

Influence of pH on the chemical degradation rate of citral in aqueous solutions: the degradation rate increases with decreasing pH (Choi et al 2009). .AC C EP TE D M AN U SC RI PT ACCEPTED MANUSCRIPT Figure 8.

microfluidizer and continuous ultrasonic homogenizer M AN U SC Droplet disruption Droplet disruption AC C EP TE D High Pressure Valve Homogenizer Continuous Ultrasonic Homogenizer Microfluidizer Droplet disruption .ACCEPTED MANUSCRIPT RI PT Figure 9: Schematic representation of mechanical devices that can be used to produce beverages emulsions using the high-energy approach: high pressure valve homogenizer.

ACCEPTED MANUSCRIPT RI PT Figure 10: Schematic representation of various methods that can be used to produce beverages emulsions using a low-energy approach: emulsion inversion point method. T > PIT W/O O/W/O O/W AC C EP TE D Emulsion inversion point method M AN U SC W/O Emulsion Cool T = PIT Bicontinuous Microemulsion Heat T < PIT O/W Emulsion Spontaneous emulsification method PIT method . spontaneous emulsification and phase inversion temperature.

ACCEPTED MANUSCRIPT AC C EP TE D M AN U SC RI PT Figure 11: Influence of homogenization pressure in a microfluidizer on the mean droplet diameter of oil-in-water emulsions stabilized by either β-lactoglobulin (BLG) or sodium dodecyl sulfate (SDS). . McClements 2011). The oil phase density was increased by adding increasing amounts of weighting agent (Qian.

.ACCEPTED MANUSCRIPT AC C EP TE D M AN U SC RI PT Figure 12: Influence of surfactant-to-oil ratio on the formation of 20 wt% oil-in-water emulsions stabilized by a non-ionic surfactant (Tween 80) prepared using the spontaneous emulsification method (Sabeti. Fang. and McClements 2012). The oil phase consisted of 80% vitamin E acetate and 20% MCT.

ACCEPTED MANUSCRIPT Figure 13: Schematic diagram of formulation-composition map for a typical surfactant-oil-water system. This map can be used to understand the formation of emulsions and nanoemulsions suing various phase inversion methods. RI PT W/O/W M AN U SC W/O Transitional TE D O/W O/W/O AC C EP Catastrophic • HLD – Hydrophilic-Lipophilic Deviation • Relative affinity of surfactant for water and oil phases (surfactant & system dependent) • WOR – Water-to-Oil Ratio • Depends on system composition .

A very fine transparent nanoemulsion is formed when the system is heated.. 13% Tween 80.ACCEPTED MANUSCRIPT AC C EP TE D M AN U SC RI PT Figure 14: Change in turbidity when a coarse lemon oil emulsion (10% lemon oil. and then cooled below its phase inversion temperature. (Rao and McClements 2010) . 77% water) is heated and cooled.

2012). Weiss and McClements. .ACCEPTED MANUSCRIPT AC C EP TE D M AN U SC RI PT Figure 15: Influence of oil type on mean droplet diameter in emulsions produced using the emulsion inversion point (EIP) method by titrating water into an oil-surfactant mixture (Ostertag.

05% citral dispersed in citrate buffer solutions (Choi et al 2009).ACCEPTED MANUSCRIPT AC C EP TE D M AN U SC RI PT Figure 16: Influence of pH and storage time on the chemical degradation of 0. . The citral chemically degrades rapidly at acidic pH values.

ACCEPTED MANUSCRIPT AC C EP TE D M AN U SC RI PT Figure 17: Influence of oil droplet concentration on the chemical degradation of citral dispersed within MCT oil-in-water emulsions (Choi et al 2009). and therefore the less oil present the faster the degradation rate. . The citral chemically degrades more rapidly in an aqueous than an oil environment.

The mass fraction of citral in the aqueous phase decreases as the oil concentration increases.ACCEPTED MANUSCRIPT AC C EP TE D M AN U SC RI PT Figure 18: Influence of oil droplet concentration on the partitioning of citral within MCT oil-in-water emulsions (Choi et al 2009). .

AC C EP TE D M AN U SC RI PT ACCEPTED MANUSCRIPT Figure 19: Influence of emulsifier concentration on the mean particle diameter produced using a microfluidizer using either whey protein isolated (WPI). modified starch (MS) or gum arabic (GA) are emulsifiers under standardized conditions. .

.AC C EP TE D M AN U SC RI PT ACCEPTED MANUSCRIPT Figure 20: Influence of pH on the particle size and charge produced using a microfluidizer using either whey protein isolated (WPI). modified starch (MS) or gum arabic (GA).

AC C EP TE D M AN U SC RI PT ACCEPTED MANUSCRIPT Figure 21: Influence of ionic strength on the particle size and charge produced using a microfluidizer using either whey protein isolated (WPI). . modified starch (MS) or gum arabic (GA).

Pepper Snapple Group 5. October 2011. “Worldwide 100”.1 PepsiCo 21.4 Kraft Foods 8. Pages 44-48). SC Annual Sales (Billions of Dollars) M AN U Company RI PT Executive.6 AC C EP TE D Coca-Cola Co.8 Dr. .ACCEPTED MANUSCRIPT Table 1: Global revenue from non-alcoholic beverage sales by major beverage manufacturing companies in 2010 (Beverage 35.

ACCEPTED MANUSCRIPT Table 2. Sign Magnitude Range Factors Affecting Van der Waals Attractive Intermediate Intermediate Always present Steric Repulsive Strong Short Thickness and chemistry of interface SC Interactions Repulsive Strong-to-Weak Long-to-Short pH and ionic strength Depletion Attractive Weak-to-Medium Short Amount & type of non- M AN U Electrostatic adsorbed polymer Short TE D Attractive Strong Strong Long EP Hydrophobic Attractive AC C Bridging Amount & type of adsorbing polymer Surface hydrophobicity . It is assumed that the RI PT droplets are coated by the same type of emulsifier. Summary of major colloidal interactions operating between oil droplets in beverage emulsions.

2005). and weighting agents commonly used in the formulations of reported. McClements. The restriction levels based on USA regulations are also Esterification of Sucrose with Acetic and Isobutyric Anhydrides . Physicochemical properties of oil phase.ACCEPTED MANUSCRIPT Table 3. 2000. Density (kg m-3) Restriction Level (ppm) - ≈1050 - - ≈1000 - Yes Yes 840-850 900-920 - No 1240-1330 15 Yes 1060 Defined by manufacturer 1080 Not approved for use in the United States 100 No 1146 300 Structure Natural SC Components Oil Phases Flavor Oils Vegetable Oils Mainly Terpenes Mainly Triglycerides Weighting Agents Ester Gum Sucrose Acetate Isobutyrate EP Dammar Gum Brominated Hydrocarbon Chain of Triacylglycerols Exudate from Caesalpinaceae and Dipterocarpaceae shrubs Hydrophobic Polymer AC C Brominated Vegetable Oil TE D Low calorie M AN U Aqueous Phases Sugared RI PT beverage emulsions (Chanamai & McClements. water phase.

7 4.6 6. and Rahn-Group.6 14.3 AC C EP TE D M AN U Surfactant Sucrose monopalmitate Sucrose monostearate Sucrose distearate Sucrose polystearate Tween 20 (Polyoxyethylene Sorbitan Monolaurate) Tween 40 (Polyoxyethylene Sorbitan Monopalmitate) Tween 60 (Polyoxyethylene Sorbitan Monostearate) Tween 80 (Polyoxyethylene Sorbitan Monoooleate) Q-Naturale (Quillaja saponin) Span 20 (Sorbitan monolaurate) Span 40 (Sorbitane monopalmitate) Span 60 (Sorbitan monostearate) Span 80 (Sorbitan monooleate) RI PT Table 4.7 4. HLB numbers of selected small molecule surfactants and co-surfactants that could be used to produce beverage emulsions. National Starch. Information from various sources: McClements (2005).9 15 >9 8. .com.ACCEPTED MANUSCRIPT SC HLB Value 16 15 6 2 16 15.

Adapted from Matalanis et al (2011). Linear/Helical (High MW) Glucose and modified Glucoses Neutral or Negative Negative Negative Negative Glucose (backbone) . Summary of molecular characteristics of some common food-grade polysaccharides. Invertebrates Linear Acacia Sap Branched Coil Domains on Protein Scaffold Carob seeds Linear Linear Modified Starch Waxy Maize Linear Glucose with some nonpolar branches Plant Cell Walls Xanthomonas campestris exudate Highly Branched Coil Glucuronate (backbone) AC C Wood Pulp Xanthan Gum Negative Neutral Galactose and mannose Modified Celluloses Pectin Positive Galactose TE D Locust bean gum Negative Glucosamine EP Gum Arabic Negative M AN U Alginate Mannuronic & Guluronic Acids Charge SC Name RI PT Table 5.ACCEPTED MANUSCRIPT Source Main Structure Type Major Monomer(s) Algal Linear Carrageenan Algal Linear/Helical Sulfated Galactose & Anhydrogalactose Chitosan Crustaceans.

Tropical Citrus Vitamin Water Coca-Cola Multi-V .ACCEPTED MANUSCRIPT Table 6. Cane Sugar. Cane Sugar 120 GA EG No Coca-Cola RTD Fructose. Rebiana 0 GA EG No Beverage Sweetener Type System Half and Half Iced Tea Lemonade Arnold Palmer AriZona RTD HFCS. BVO No APM. Cane Sugar 120 GA EG No Coca-Cola RTD Fructose. Emulsifier Weighting Natural Agent Claim 50 GA None Listed No 0 GA None Listed No Cane Sugar 70 GA EG Yes Cane Sugar 70 GA EG Yes HFCS 80 GA EG No HFCS 80 GA EG No RTD HFCS 80 GA EG No RTD HFCS 80 M-FS MCT. Examples of the composition and calorie content of some commercial beverage products currently on the market.Lemonade Vitamin Water Essential Orange-Orange Vitamin Water Squeezed Lemonade Vitamin Water Zero TE D EP AC C SC Manufacturer M AN U Brand RI PT Calories (per 8 oz. M-FS EG No Coca-Cola RTD Erythritol. Ace-K 0 GA EG. SAIB No RTD HFCS 120 M-FS EG. Sucralose. Ready to Drink) Product . Sorbitol 120 GA. BVO No RTD Fructose. Ace-K Half and Half Iced Tea Lemonade Arnold Palmer Zero AriZona RTD Sucralose Cherry Citrus BodyArmor Body Armor Nutrition RTD Tropical Mandarin BodyArmor Body Armor Nutrition RTD Lemon Lime Xion4 (Powerade) Coca-Cola RTD Orange Xion4 (Powerade) Coca-Cola RTD Strawberry Lemonade Xion4 (Powerade) Coca-Cola Sour Melon Xion4 (Powerade) Coca-Cola Orange Soda Fanta Coca-Cola Original Citrus Fresca Coca-Cola RTD Energy .

Pepper Snapple RTD Sucrose 120 GA None Listed Yes Orange Mango Nantucket Nectar's Dr.ACCEPTED MANUSCRIPT Sunkist Dr. BVO No Pineapple Orange Guava Nantucket Nectar's Dr. Ace-K 0 GA SAIB No Orange Tangerine MiO Kraft Foods LC Sucralose. Ace-K 0 GA EG No Citrus Soda Sun Drop Dr. Pepper Snapple RTD Sucrose 100 GA EG Yes Lemonade Farmer's Daughter The Farmer's Cow RTD Cane Sugar 120 GA EG Yes Strawberry Lemonade Farmer's Daughter The Farmer's Cow RTD Cane Sugar 110 GA EG Yes Lemonade MiO Kraft Foods LC Sucralose. Pepper Snapple RTD Sucrose 120 GA None Listed Yes Strawberry Kiwi Snapple Dr. Pepper Snapple RTD APM. Pepper Snapple RTD HFCS 110 M-FS EG No Orange Diet Crush Dr. BVO No SC M AN U TE D EP AC C RI PT Orange Soda . SAIB No Lemon-Lime G2 of Gatorade G-Series PepsiCo RTD Sucrose 80 GA EG No Orange G2 of Gatorade G-Series PepsiCo RTD Sucrose 80 GA EG. Ace-K 0 GA SAIB No Sparkling Lemonade N/A Lorina RTD Sucrose 90 GA EG No Pink Citrus Lemonade N/A Lorina RTD Sucrose 120 GA EG No Lemonade G2 of Gatorade G-Series PepsiCo RTD Sucrose 80 GA EG. Pepper Snapple RTD HFCS 120 GA EG.

Ace-K 0 GA BVO No Nature's Blends Poland Spring RTD Cane Sugar 50 GA EG Yes Orange Cranberry Tangerine Skinny Water Skinny Nutritional RTD Sucralose. Ace-K 0 GA EG No Old-Fashioned Lemonade N/A Zeigler's Beverages RTD Sucrose 100 GA EG No SC Key: Ace-K Acesulfame Potassium APM Aspartame BVO Brominated Vegetable Oil EG Ester Gum GA Gum Acacia HFCS High Fructose Corn Syrup Liquid Concentrate LC Medium Chain Triglycerides MCT M-FS RTD SAIB M AN U Lemon TE D Diet Mtn Dew RI PT PepsiCo EP N/A ModifiedFood Starch AC C Mtn Dew Ready to Drink Sucrose Acetate Isobutyrate .ACCEPTED MANUSCRIPT RTD HFCS 110 GA BVO No N/A PepsiCo RTD APM.

21 CFR 101. but regarded as a product lacking any synthetic N/A Any substance that imparts flavor that is not derived from its natural “Artificially Flavored” 21 CFR 101.30(j).54(e) 40 cal or less per RACC. Brix table in 21 CFR 101.30(h)(1) as the basis for 100% juice. SC Undefined. 21 CFR 101. 21 CFR 101. Source 21 CFR 101. calculate use-percentage from the 21 CFR 101.ACCEPTED MANUSCRIPT Claim Justification “0 Calories” Less than 5 cal per RACC.54(b) TE D “Contains % Juice” “Excellent Source of Vitamin” “Low Calorie Soda” “Low Sodium” Contains 10%-19% of the DV per RACC. For juice made from concentrate. Claims and justifications that can be made on beverage products.30(h) Contains 20% or more of the DV per RACC. 21 CFR 101. 21 CFR 101. RI PT Table 7.61 AC C “Good Source of EP Vitamin” .60(b) “All Natural” M AN U components.22 (a) (1) source.60(b) 140 mg or less per RACC.

22 (a) (1).ACCEPTED MANUSCRIPT 21 CFR 101. “Natural and Artificial Contains Natural and Artficial Flavors. At least 25% less sugars per RACC than an appropriate reference food.22(k)(1) (2). not solely as a “Naturally Flavored” 21 CFR 101.65 (b)(2) 21 CFR 101. 21 CFR (g) 101.65(b)(1) Cannot Contain Pulp. beverage. “No Pulp” “Reduced Sugar” EP 21 CFR 101. 21 CFR 101.22 (a) (3) No Sugar or Sugar-Containing Ingredients are added during processing.22 (3) The flavor constituents function in the food as flavor. Natural color is considered artficial color when used for 21 CFR 74 TE D colorant purposes.65(b)(1) Cannot Contain Preservatives. AC C “No Preservatives” 21 CFR 101. RI PT Flavor” 21 CFR 101.65 (b)(2) 21 CFR 101. 21 CFR 101.22 (a) (3). “No HFCS” 21 CFR 101.60(c) (2) Contains no colarant source outside the principle flavor components of “No Artificial Colors” 21 CFR 101.65(b)(1) Cannot Contain HFCS.60 (c) .65 (b)(2) 21 CFR 101. M AN U “No Added Sugar” SC source of nutrition are derived from its natural source in nature.