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Comprehensive Scalping of

Reviews Flavors in
in Packaged Foods
Food Science
and M.G. Sajilata, K. Savitha, R.S. Singhal, and V.R. Kanetkar

Food Safety
ABSTRACT: Food packaging, although an integral part of the food chain, has a major drawback in that, often, the
packaging material interacts with the flavor constituents of the food, causing either a selective or an extensive loss
of desirable food flavors or absorption of undesirable off-flavors from the packaging material, thereby resulting in
an eventual loss of quality of the packaged food item. The process is called “scalping” and is of great concern to the
food industry, which is always looking out for new avenues in “packaging solutions” for its final product quality
needs. The review highlights the various attributes of the scalping process, explores approaches to the reduction of
the manifested undesirable effects, and covers other relevant aspects.

Introduction polyethylene (HDPE), polypropylene (PP), polyethylene tereph-


Food packaging in recent years has experienced rapid ad- thalate (PET), aluminum sheet (Surlyn), ethylene vinyl alcohol
vances and continuous growth due to consumer desire and de- copolymer (EVOH), and others (Gremli 1996). Figure 1 shows
mand for conveniently packaged products. This has promoted a the molecular structures of the polymers used as packaging ma-
trend in packaging materials that has evolved from simple food terials (Willige 2002). Among the plastic materials, polyethylenes
wraps to sophisticated containers. Besides providing an adequate and polypropylenes (homo- and copolymers) are mostly used in
shelf life and product quality it is desirous that the packaging package design preferred for contact with the product both in
material also participates in the overall flavor management of monolayer and laminated or coextruded structures because of
the packaged food, flavor being an underlying factor in the con- their good chemical resistance and inertness to most foods, good
sumer acceptability of all food products. However, sorption of barrier properties to water, and thermosealability. However, their
food aromas, particularly by plastic packaging materials, is usu- polyolefinic nature gives them high lipophilicity enabling reten-
ally perceived as a major factor contributing to the quality alter- tion of large amounts of nonpolar compounds such as most of
ation of most foods during storage. This causes changes in both the aroma compounds, thereby causing an aroma imbalance in
the intensity and characteristics of the food flavors owing to their the packaged food. Trace concentrations of residual solvents,
absorption by the packaging material, a phenomenon commonly monomers, plasticizers, inhibitors, or mold-release agents con-
referred to as “scalping” (Roland and Hotchkiss 1991). ceivably could migrate to the food product and, also, flavor in-
Flavor scalping is a term used in the packaging industry to gredients can travel to the package. Moreover, flavor scalping
describe the loss of quality of a packaged item due to either its from the product does not require the product to be in direct con-
volatile flavors being absorbed by the package or the food absorb- tact with the polymer because the aroma compounds are volatile
ing undesirable flavors from the packaging material. The inability enough to transfer from the headspace to the package. Thus, al-
to prevent scalping is a sore point for many packagers, a classic though the polymeric films may be adequate moisture or gas bar-
example being the absorption of various plastic flavors when soft riers for a product, these benefits can be offset by flavor scalping.
drinks are stored in plastic bottles for an extended period of time. Studies in scalping will therefore help determine the type of plas-
Tropicana discovered that its gable-topped orange juice cartons tic films best suited for a particular food product (Risch 1991).
scalped flavor from the juice by absorbing important chemicals. The frequent use of PE on the inner surface of the food-contact
Polyethylene (PE), the most common plastic used in commercial polymer containers has made it the principal polymer in most
products, including beverages, is a top scalper. scalping studies.
Commercial plastics for food packaging include simple ho-
mopolymers or copolymers such as low-density polyethy- Interaction between Food Flavor and Packaging Material
lene (LDPE), medium-density polyethylene (MDPE), high-density The first and foremost function of a food package is to pro-
tect the product and preserve its inherent quality (Nielsen and
Jägerstad 1994). Over the past decade, the use of plastic pack-
MS 20060142 Submitted 3/1/2006, Accepted 9/18/2006. Authors are with Food ages has increasingly replaced metal and glass for food and bev-
Engineering and Technology Dept., Inst. of Chemical Technology, Univ. of erage packaging, the advantages being numerous—lower costs,
Mumbai, Matunga, Mumbai-400 019, India. Direct inquiries to author Singhal
(E-mail: rekha@udct.org). lighter in weight, less apt to shatter, transparent, flexible, and
convenient to the consumer. In spite of all these advantages,

C 2007 Institute of Food Technologists Vol. 6, 2007—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 17
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
there are some properties of plastics that limit their use in food occurring by permeation or migration through the package or
packaging (Salame 1989). Food packaging interactions, defined those from sorption by the container (Strandburg and others
as an interplay between food, packaging, and the environment, 1991).
can produce an adverse effect on the food and/or the package
(Hotchkiss 1997). Interactions between the plastic package and
the flavor constituents can cause adsorption and absorption of fla- Modeling Studies in Flavor Scalping
vor volatiles by the packaging material, permeation of the flavor There are several models, more aptly theoretical considera-
volatiles through the plastic material, food- and flavor-induced tions, to predict the losses due to flavor scalping. Flavor losses
changes in the physical properties of the plastic polymer, as well that result from interaction with the polymer package can be
as interactions of low-molecular-weight compounds in the plastic either losses occurring by permeation or migration through the
such as solvent and plastifiers with the food flavor or the food it- package or those from sorption by the container (Strandburg and
self, thereby resulting in an overall imbalance in the flavor profile others 1991).
of the food (Gremli 1996). The permeation process can be described as a multistep event.
Figure 2 shows the possible interactions between foodstuff, First, collision of the penetrant molecule with the polymer is fol-
polymer film, and the environment and their adverse conse- lowed by sorption into the polymer. Next, migration through the
quences (Nielsen and Jägerstad 1994). Flavor losses that result polymer matrix occurs and, finally, desorption of the permeant
from interaction with the polymer package can be either losses from the polymer completes the process. For a polymer with thin
film geometry, Fick’s first law can be written as

Mx
= P Apx
t L
where M x /t is the transport rate of the material x through a film
of area A, with a thickness of L, and under a chemical potential
created by pressure difference across the film of p x . P is the
permeability coefficient and is a steady-state parameter.

P = DS

The permeability consists of 2 parameters, the diffusion coeffi-


cient (D) and the solubility coefficient (S). The diffusion coeffi-
cient is a kinetic parameter. It is a measure of how fast trans-
port events will occur. It reflects the ease with which a penetrant
molecule moves within a polymer host. The diffusion coefficient
is determined from the following equation:

L2
D=
7.2t1/2

where L is the film thickness and t 1/2 is the time required to reach
one-half the steady-state mass transport rate. Once the permeabil-
ity coefficient and the diffusion coefficient have been obtained,
Figure 1 --- Molecular structures of polymers the solubility coefficient can be calculated.
The solubility coefficient is a thermodynamic parameter. It is a
measure of the concentration of penetrant molecules that will be
in position to migrate through the polymer.

C x = Spx

where C x is the concentration in the polymer and p x is the partial


pressure of x in the vapor phase.
The sorption of the flavor ingredient from solution onto the
polymer involves the process of partitioning and diffusion. The
mechanism of sorption consists of both adsorption onto the solid
surface followed by dissolution into the polymer and diffusion
away from the surface under the driving force of a concentration
gradient until equilibrium is established. The partitioning step in-
volves adsorption onto the polymer surface and mixing into the
polymer matrix, which depends on the relative forces of attrac-
tion between the solution and the polymer for the solute. These
forces are governed by the thermodynamics of the system and are
Figure 2 --- Possible interactions between foodstuff, poly- affected by structure and polarity. These factors can be consid-
mer film, and the environment and their adverse conse- ered on the basis of cohesive energy density (CED) forces or its
quences (Nielsen and Jägerstad 1994) square root, the solubility parameter of the Hildebrand equation.
18 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 6, 2007
Scalping of flavors in packaged foods . . .

The Hildebrand approximation for the heat of mixing is scribe approximately the migration of a substance from a polymer
into a food (simulant) for situations where m F, t /m F, e < 0.5:
Hm = v1 (δ1 − δ2 )22
mF,t = 2kcP ,0 (DP t/π)1/2
where H m is the partial molar heat of mixing, v 1 is the partial
molar volume of the penetrant,  2 is the volume fraction of the D P is the actual diffusion coefficient of the migrant in the polymer
polymer in the mixture, and δ 1 and δ 2 are the square roots of the with a homogeneous distribution of the migrant at an initial con-
CED of the penetrant and the polymer. The differences in the CED centration, c P ,0 . The constant k is the measure of the influence
values of the polymer-penetrant combination in a given system of factors that lie outside the polymer/migrant system and has,
will affect the size of heat of mixing and a permeant with a larger by definition, a value of k = 1 in the absence of such influences
CED will have larger heat of mixing and less negative G than (such as for contact with ethanol and oil) as long as no poly-
the one with a smaller CED. The diffusion step depends on the mer swelling takes place. A practical application of this equation
mobility of the solute, which can depend on its size and interac- is that for cases with k = 1, the actual diffusion coefficients of
tion with the polymer to plasticize and relax its chain segments migrants in the polymer can be determined from the kinetic mea-
(Halek and Luttman 1991). surement of m F , t from systems with known/measured values for
Organic vapors often solvate host polymers that eventually ex- c P ,0 . Provided that the migration potential in the polymer, that is,
hibit increased permeability to oxygen and other gases suggesting the initial amount of migrant dissolved in the polymer, m P ,0, is
that oxygen permeability might provide information on volatile known, then
scalping (Salame and Steingiser 1977). In one study, limonene
absorption by LPDE increased oxygen permeability, which was mP ,0
proportional to the limonene concentration (Sadler and Braddock mF,e =
1990, 1991). As oxygen permeability is directly proportional to 1 + kP ,F (VP /VF )
penetrant concentration, M t /M α will equal P t /P α , where M t and
P t are, respectively, the absorbed volatile weight and oxygen per- where
meability of the polymer at time t, and M α and P α are the cor- cP,e
responding volatile weight and polymer oxygen permeability at kP ,F =
t = α. If results are expressed as a dimensionless ratio, then oxy- cF,e
gen permeability can be used to solve mass transfer equations.
Crank (1967) presented an applicable equation for membrane The partition coefficient k P , F is defined as the concentration ratio
absorption and desorption (Sadler and Braddock 1990), where at equilibrium of a migrant in the polymer, c P , e , divided by that
at equilibrium in the foodstuff or food stimulant, c F , e . The values
 {8 exp{ − D(2n + 1)2 π 2 t}}/(2n + 1)2 π 2 } for k P , F range over several orders of magnitude, depending on
(Mt /Mα )desorption = the polarity of the polymer involved, the food simulant, and the
n→0 to α
4τ 2 nature of the migrant. The k P , F value for limonene, a nonpolar
substance in the LDPE/water system at 23 ◦ C, was found to be
and the absorption equation is (M t /M α ) absorption = 1– higher than 5000. This makes it retained in the polymer, whereas
(M t /M α ) desorption , where D is the diffusion coefficient, and τ a much more polar compound such as cis-hexenol shows a much
is 12 the membrane thickness when both surfaces are exposed to lower value of 0.33, causing considerable transfer into water.
the penetrant. For single-surface penetrant exposure, τ is the full In recent years, the possibility of modeling with easily available
thickness of the membrane. hardware and software opens a large field of complex applica-
Migration testing using food simulants is the normal procedure tions. MIGRATEST Lite (1997, 1999), COATING TEST (1999), and
for checking compliance of a food packaging material against MIGRATEST (2000) are specialized softwares offered for migra-
specific migration limits (SMLs). However, as Feigenbaum and tion modeling (Brandsch and others 2000).
others (2002) point out, this is not practical for several reasons.
Industries that put packaged foods or materials intended for food
contact on the market do not know the identity of the potential Sorption of Food Flavors by the Packaging Materials
migrants; sometimes, those who manufacture and sell these raw Sorption of food flavors in polymers involves the process of
materials do not know the processing conditions or the final ap- both partitioning and diffusion. Moreover, although the intensity
plication; and even if the identity of the migrants were known of aroma of a packaged foodstuff depends on the vapor pres-
it may be difficult to analyze them. Therefore, the use of math- sure (influenced by the other food components), interaction of
ematical modeling to predict migration, which can reduce the the volatile organic moieties with other food constituents, and
amount of tests to be undertaken, has been recently introduced aroma barrier characteristics of the package (Mahoney and oth-
into legislation. Practical examples for the application of this new ers 1988), the nature of the aroma is also imperative in deter-
concept are described in the Practical Guide (European Commis- mining the extent of sorption. The extent of flavor absorption is
sion 2003). influenced by the properties of the polymer, the flavor molecules,
Mass transfer from a plastic into food consists essentially of ki- and also external conditions. The chemical composition, chain
netic (diffusion in the polymer and foodstuff) and thermodynamic stiffness, morphology, polarity, and crystallinity of the polymer in-
(equilibrium partitioning between the packaging and food) fac- fluence flavor absorption as much as the chemical composition,
tors, besides the geometric dimensions of a given food/packaging concentration, and polarity of the flavor compounds, as well as
system. The most important variables that control migration of the the presence of other chemical constituents. External factors such
substances are contact time t and temperature T . Numerous mi- as duration of storage, relative humidity, temperature, and the
gration tests have shown that the majority of measurements could presence of other food components can also affect the solubility
be represented as being approximately proportional to the square of aroma compounds in a polymer (Nielsen and others 1992a;
root of time t and the initial concentration of the migrant in the Leufven and Hermansson 1994).
polymer, c P ,0 . With the assumption that material transport obeys Some of the major factors influencing the scalping process are
the law of diffusion, the following equation can be applied to de- described in detail below.
Vol. 6, 2007—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 19
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
Flavor Characteristics

Concentration
The higher the concentration of the sorbed material, the higher
the rate of transport into the polymer structure (Brody 2002). The
presence of copermeants can affect the rate of transport of the
molecules through the polymer usually by increasing the rate.
Carbon chain length, boiling point, and polarity
The carbon chain length is closely related to the boiling point
of a molecule, and several researchers have indicated a relation-
ship between solubility and boiling points of sorbates. Thus the
carbon chain length of volatiles affects their solubility in polymer
films. In a sorption study, permeation and diffusion of volatile Figure 3 --- Structure of linalool
compounds into PE or ethylene vinyl copolymer films were eval-
uated using volatile compounds such as alkanes, aliphatic ethyl
ethers, aldehydes, and alcohols containing 4 to 10 carbon atoms. its higher boiling point (198 ◦ C for linalool, 175 ◦ C for limonene)
Sorption and solubility coefficient were found to increase with an is indicative of its ability to condense and remain within the ma-
increase in the carbon chain length of the volatile compounds. A trix (Roland and Hotchkiss 1991). Boiling point has been corre-
study on the sorption behavior of flavor compounds by PE liner lated to higher solubility by several workers. Also, linalool, usu-
of laminated pouches (PET/Al/PE) containing 43 volatile com- ally present at 1/10 the concentration of limonene, may have a
pounds showed the distribution ratio of the flavor compounds greater potential in affecting aroma due to sorption by a PE pack-
to increase with carbon chain length of the flavor compounds age than limonene. The higher solubility of linalool coupled with
from 0.01 to 0.1 for alcohols, 0.03 to 1.23 for aldehydes, 0.02 to its higher sensory impact increases the effect of linalool sorption.
5.77 for aliphatic esters, and 0.11 to 11.6 for benzoates (Shimoda Figure 3 and 4 differentiates linalool and limonene with respect
and others 1988). The distribution ratio, defined as the ratio of to their structures.
amount sorbed into PE film and the adhesive layer to the amount Solute polarity is one of the predominant controlling factors
remaining in the solution with respect to each flavor component, influencing sorption. Flavors are absorbed more easily in a poly-
was used as the basis of comparison. In each series, the distri- meric film of similar polarity. The sorption of a number of cit-
bution ratios increased about 3-fold for each methylene group, rus flavors by LDPE is almost instantaneous, the partitioning
but in the compounds composed of 11 or more carbon atoms, depending on the polarity of the compounds. Comparing car-
the increments were either less or, in the case of aldehydes, neg- vone (C 10 H 14 O) and limonene (C 10 H 16 ), both similar terpenes
ative. The sorption of esters, ketones, and aldehydes by PP has but with different polarity, it has been shown that the less po-
also been shown to increase as the number of carbon atoms in the lar limonene is not only sorbed at a faster rate but also dif-
compounds increased. Moreover, compounds with 8 or more car- fuses more rapidly, probably due to lesser cohesive forces (Halek
bon atoms were demonstrated to be sorbed from yogurt drinks by and Luttman 1991). In the sorption of citrus oil constituents by
HDPE with shorter molecules remaining in the product (Linssen polyolefins, terpenes showed the highest affinity for the poly-
and others 1991). In the same study, it was observed that highly mers, followed by sesquiterpenes (C 15 ); larger amounts of es-
branched molecules were sorbed to a greater extent than linear ters and aldehydes were sorbed than alcohols, due to polarity
molecules. (Charara and others 1992). For the same reasons, saturated alde-
Esters and aldehydes are reportedly absorbed much more than hydes were sorbed to a greater extent than those with double
the alcohols in LDPE. The absorption of aldehydes has been cor- bonds.
related to their structure, the shorter chain aldehyde, decanal, be- Orange juice aromas have been demonstrated to be sorbed to
ing absorbed to a lesser extent than the C 12 aldehyde, and dode- different extents, starting with hydrocarbon compounds, which
canal. The chain length of the lipophilic portion of the molecule showed the highest affinity to LDPE, followed by ketones, esters,
appears to affect its absorption, the unsaturated aldehydes (for aldehydes, and finally alcohols (Linssen and others 1991; Nielsen
example, perillaldehyde and geranial) being absorbed to a lesser and others 1992a; Linssen and Roozen 1994). Factors that affect
extent than the saturated aldehydes (Charara and others 1992). absorption include molecular size of the aroma compounds and
The length of the carbon chain might account for the differences polarity and solubility properties of both the polymer and the
between the esters; the longer the chain, the lesser the polarity aroma compounds. Table 1 shows the solubility parameters and
and ease of absorption of the compounds by the nonpolar poly- hydrogen-bonding characters of aroma compounds and the poly-
olefins. mers used in the study by Nielsen and others (1992b). In general,
According to Shimoda and others (1988), the effect of func- the smaller the difference between δ values of the polymer and
tional groups on the distribution ratios of flavor compounds be- the flavor compound, the greater the solubility of the flavor into
tween a film and a solution was greater in the liquid phase the polymer. Alcohols have much larger solubility parameter val-
because of closer interactions, whereas the effect of molecular ues than LDPE, LLDPE, and PP, which might explain why they
weight or boiling point was much larger than the functional group
in the vapor phase. Strandburg and others (1991) obtained a linear
relationship between the logarithm of the solubility coefficient in
vinylidene chloride copolymer and the boiling point of linear es-
ters, alkanes, and ketones. Similar results are reported for the sol-
ubility of alkyl esters in polyvinyl alcohol (Landois and Hotchkiss
1988). The higher solubility of linalool compared to limonene in
PE is also shown to be influenced by its boiling point. Linalool is
a more linear, less bulky molecule than limonene, which would
facilitate its ability to move into the polymer matrix. In addition, Figure 4 --- Structure of limonene

20 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 6, 2007


Scalping of flavors in packaged foods . . .

are less absorbed compared to esters and aldehydes while PET and others 1999). Polyolefins are highly lipophilic and are incom-
has a solubility parameter closer to that of the alcohols. Also, po- patible for packaging products with nonpolar substances (such as
larity and hydrogen-bonding character play an important role in fats, oils, aromas) since they can be absorbed and retained by the
the prediction of solubility. The reason why the alcohols are not package (Hernandez and others 2001). The polyesters, however,
absorbed to a greater extent into PET might be due to their strong are more polar than the polyolefins and hence show less affinity
hydrogen-bonding character, which PET lacks. Esters and alde- for the nonpolar components. Table 2 shows the approximate up-
hydes have solubility parameters very close to LDPE, LLDPE, and per and lower limits for partition coefficients one may normally
PP, which partly explains their large partition coefficient in these encounter in plastic/food systems based on the polarities of the
polymers. The differences between the esters might be accounted solutes, plastics, and foods (Baner 2000a). It also shows the ap-
for by the length of the carbon chain—the longer the chain, the proximate ranges of partition coefficient values for various solutes
less polar the compounds, facilitating easier absorption by the between typical food-contact plastics and liquid phases.
nonpolar polyolefins (Nielsen and others 1992b). LLDPE and oriented polypropylene (OPP) (both nonpolar)
have been shown to easily absorb limonene and myrcene and,
Polymer Characteristics to smaller extents, decanal, hexyl acetate, nonanone, carvone,
linalool, octanol, and hexanal (Willige and others 2002a). The
flavor molecules carvone and limonene have similar structure but
Surface area limonene is a nonpolar terpene, while carvone is an oxygenated
The degree of sorption is directly related to the available surface polar terpene. Hence, limonene is absorbed in larger quantity
area in contact with the food (Gremli 1996). than carvone.
Polarity Glass transition temperature
Different plastic materials have different polarity, hence they Sorption rates to a certain extent depend on the glass transition
differ in their affinity toward the flavor compounds. Flavors are temperature (T ) of the polymer that determines the flexibility of
g
absorbed more easily in a polymeric film of similar polarity (Gallo the polymer molecules. Below T g , the polymer molecules are stiff
(glassy state) and the chance of a flavor molecule finding a suffi-
Table 1 --- Solubility parameters (δ values) ciently large void is limited. Above T g , the polymer molecules are
highly flexible (rubbery state), which makes this chance higher.
Compound/ δ Hydrogen-bonding Table 3 shows the glass transition temperatures of polymers com-
polymer values (H) character monly used for food packaging.
Rubbery polymers such as the polyolefins PE and PP, which
Ethyl butyrate 8.5 Moderate have a T g below ambient temperature, have a high diffusion
Butyl acetate 8.5 Moderate coefficient for flavors with steady-state permeation being estab-
Isopentyl acetate 7.8 Moderate lished quickly in such structures (Giacin and Hernandez 1997).
Ethyl-2-methyl butyrate 8.3 Moderate Stiff-chained polymers that have a high glass transition temper-
Butyl propanoate 8.8 Moderate ature generally have low permeability, unless they also have a
Hexyl acetate 8.6 Moderate high free volume (Miller and Krochta 1997). Polymers such as
Hexanal 8.3 Moderate the polyesters PET, PC (polycarbonate), and PEN (polyethylene
Trans-2-hexenol 8.5 Moderate naphthalate) have a T g above ambient temperature. At room tem-
Isopentyl alcohol 10 Strong perature, these glassy polymers have very stiff chains and a very
Hexanol 10.7 Strong low diffusion coefficient for flavor molecules at a low concen-
Low-density polyethylene 8 Poor tration. Glassy polymers such as polyvinylidene chloride have a
Linear low-density polyethylene 8 Poor low diffusion coefficient for aroma molecules at a low concen-
Polypropylene 9.2 Poor tration and hence display high flavor-barrier properties (Brody
Polyamide 11.1 Strong
Polyester 10.7 Moderate

Table 2 --- Approximate partition coefficient values for various plastic/food package systems
Substance (i) Polymer (P) Food phase (L) K P /L

Nonpolar (n-alkane) Nonpolar (PO) Very polar (water) 1× 105 –1 × 106 (40000)
Nonpolar to middle polarity (d-limonene) Nonpolar (PE) Very polar (water) 1200
Nonpolar to middle polarity (d-limonene) Nonpolar (PO) Polar (fruit juices) 400–600
Middle polarity (ketone) Middle polarity (PVC) Polar (ethanol) 10–20
Middle polarity (ester) Nonpolar (PO) Very polar (water) 10–40
Nonpolar (large n-alkanes) Nonpolar (PO) Polar (ethanol) 5
Nonpolar (n-alkane) Nonpolar (PO) Nonpolar (n-alkane) 1
All polarities All polymers Oil 0.1–10
Polar (alcohol) Very polar (PA) Very polar 1
Polar to middle polarity (alcohol and hydrocarbon) Polar (PET) Polar 0.1 --- 3
Polar (alcohol) Nonpolar (PO) Very polar (water) 0.5
Polar (alcohol) Middle polarity (PVC) Polar (ethanol) 0.1 (0.07)
Polar (alcohol and middle polarity) Very polar, polar Polar >0.1
(PA) (propanol) 0.05–0.1
(PET) (methanol) 0.001–0.05
Very polar (acid) Nonpolar (PO) Very polar (water) 0.001 (0.001)

Vol. 6, 2007—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 21


CRFSFS: Comprehensive Reviews in Food Science and Food Safety
2002). PEN has excellent performance characteristics in compar- many countries. A major problem associated with refilling is the
ison to PET for carbonated beverages, allowing hot-fill, rewash, sorption of flavors from foodstuffs by the container causing off-
and reuse, due to its high T g (VanLune and others 1997). flavors in the products filled into the same container. The extent
of sorption is dependent on temperature, the polymer type, the
Polymer crystallinity
carbon chain length, and the type of functional groups of the sor-
Morphological properties that influence permeability and dif- bate. Washing with sodium hydroxide solutions removes less than
fusivity include structural regularity or chain symmetry leading to half the sorbed amount of terpenes from plastic bottles (Gremli
3-dimensional order or crystallinity (Brody 2002). The more or- 1996). A study to evaluate the efficacy of washing of PET bottles
dered the polymer molecular structure, the lower the rate of sorp- intended for reuse with sodium hydroxide solution in order to
tion of the food aroma constituents. Crystalline regions can re- remove limonene, linalool, and linalyl acetate showed limonene
duce sorption or act as impermeable barriers for diffusion through to be significantly sorbed onto the walls of the bottles even after
the polymer. They can act as crosslinks to prevent swelling of washing (Safa 1999).
the polymer. The crystalline regions can also restrain polymer Recycling of old polymers as new bilayer bottles may be of
segmental mobility affecting the solute permeability to the amor- value if a virgin polymer layer is placed between the recycled
phous regions. Thus, the degree of sorption for a given solute is polymer and the food. The virgin polymer layer plays the role
often related to the degree of the amorphous polymer content of a functional barrier. In the case of solid foods, the process
(Charara and others 1992; Letinski and Halek 1992). PP is an ex- of contamination by the recycled polymer is controlled by ra-
ample of a crystalline polymer that can exist in various degrees dial diffusion through the bottle and the food. An increase in the
of crystallinity. volume of the bottle is associated with a decrease in the area
Absorption of limonene and myrcene by PC is found to be of the bottle–food interface per unit volume of food (Rosca and
much higher than by PET and PEN, although the T g of PC is Vergnaud 1998).
much higher than the T g of PET and PEN. This is attributed to the
lack of crystalline regions in PC, which is a totally amorphous
polymer (Nielsen 1994). External Factors
Surface polymer hydrolysis
Surface hydrolysis of ethylene-vinyl acetate copolymer can pH
alter sorption behavior. While the sorption of hydrocarbons, pH influences the sorption of aroma compounds into the pack-
ethyl octanoate, and decanal into hydrolyzed EVA film is de- aging material. pH has been shown to affect sorption by a factor
pressed, the sorption of alcohols is promoted. This is mainly at- of 40 between pH 3 and 5 for 2-hexanal into PE (Leufven and
tributed to solubility of the individual compounds (available from: Hermansson 1994). Lowering the pH to 3 increased the sorption
www.foodproductdesign.com). of alcohols into LDPE (Nielsen and others 1992a). Sorption of
limonene is shown to be 1.3 times more in LDPE at 22 ◦ C and
Polymer density at pH 5.2 than at pH 2.6 (Blain 1994). Nonetheless, a study on
The amount of aroma compounds sorbed in polymers has been limonene in orange juice showed pH to have no significant effect
shown to decrease with an increase in polymer density. The sorp- on scalping (Nielsen and others 1992a).
tion rate for limonene decreased from 75% to 63% and that of Leufven and Hermansson (1994) studied the interaction of
carvone decreased from 17% to 10% when the PP density in- aroma compounds such as trans-2-hexanal, 2-heptanone, 6-
creased from 0.8830 g/cm3 to 0.9213 g/cm3 , respectively (Gremli methyl-5-hepten-2-one, 6-methyl-5-hepten-2-ol, and limonene
1996). from tomato juice with polymers such as PET, PE, and EVOH as a
function of pH. The amount of extractable aroma compounds in
Free volume of the polymer the different polymers at all pH values decreased in the following
The free volume of a polymer is the molecular “void” volume order: EVOH > PE > PET. Between these polymers, the sorp-
that is trapped in the solid state (Salame 1989). The permeating tion of the aromas was less influenced by pH in PET than in the
molecule finds an easy path in these voids. Generally, a polymer other 2 polymers, where PE contained larger amounts of the com-
with poor symmetry in the structure or bulky side chains will pounds at pH 4 than at pH 7. For EVOH, there was an increase
have high free volume and hence high permeability. A polymer’s in sorption of d-limonene with increasing pH. Table 4 shows the
molecular configuration is altered through solvation by organic amount of added aroma compounds sorbed in the polymer films.
penetrants (Takeuchi and Okamur 1976). It is hypothesized that pH has a direct relationship with polarity,
solubility, and structure of molecules and can be influenced by
Use of recycled plastics
them.
In an effort to reduce wastes from food packaging materials,
refillable PET bottles for carbonated drinks have been adopted in
Food composition
Food constituents play an important role in influencing the
Table 3 --- Common applications in food packaging applica- sorption of flavors. Not only the type of plastic used is of
tions and their glass transition temperatures (T g ) (Helm- importance for the uptake of aroma compounds, but also the pos-
roth and others 2002) sible interactions between the flavor and food components. Fla-

vor components may be dissolved, adsorbed, bound, entrapped,
Polymer T g ( C) encapsulated, or retarded in their diffusion through the food ma-

LDPE –20
trix by food components. The relative importance of each of these
HDPE –20
mechanisms varies with the properties of the flavor chemical
PP 5
(functional groups, molecular size, shape, volatility, and so on)
PS 90–100
and the physical and chemical properties of the components in
PET 67
the food. Proteins, carbohydrates, and lipids interact with flavors,
PVC 80
changing the concentration of free flavor in solution and, con-
PC 149
sequently, affecting their absorption. Absorption of flavor com-
pounds by linear low-density polyethylene (LLDPE) was studied
22 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 6, 2007
Scalping of flavors in packaged foods . . .

Table 4 --- Amount of added aroma compound (μg cm−3 ) extracted from polymer films stored in spiked tomato juice
Days of Trans-2- 6-methyl-5 6-methyl-5-
Polymer pH storage hexenol 2-heptanone hepten-2-one hepten-2-ol Limonene

PE 4 1 11 20 44 36 605
7 20 92 298 132 848
7 1 22 77 12 55 206
7 21 21 30 45 436
PET 4 1 11 11 8 4 19
7 22 31 24.4 14 58
7 1 10 8 7 5 17
7 14 28 21 11 50
EVOH 4 1 28 50 50 155 73
7 21 28 29 89 52
7 1 28 68 81 248 122
7 45 43 43 94 81

in model systems representing differences in composition of the propionate in polyvinyl alcohol has been shown to reduce with an
food matrix. The extent of flavor absorption by LLDPE was influ- increase in RH (Landois and Hotchkiss 1988). This is attributed to
enced by food components in the order oil or fat > polysaccha- the competition between ethyl propionate and water molecules
rides and proteins > disaccharides (Willige and others 2000a). for available sorption sites.
Due to the lipophilic character of many flavor compounds, Recently, the use of EVOH materials providing a high barrier
food products with high oil/fat content tend to lose less flavor by to organic compounds is gaining much attention as a means to
absorption into LLDPE packaging than food products containing reduce food aroma scalping. However, although EVOH is an ex-
no or a small quantity of oil (Willige and others 2000b). The pres- cellent barrier to food aroma when dry, a property that even im-
ence of a relative small amount of oil (50 g/L) has been shown proves at low RH, the solubility and diffusivity of the compounds
to decrease absorption substantially. Also, proteins, particularly, increase dramatically with humidity at medium to high water ac-
β-lactoglobulin and casein, are able to bind flavors, resulting in tivity. An increase in moisture content of moisture-sensitive plas-
suppression of absorption of the flavor compounds. Polysaccha- tics such as polyamides or EVOH is reported to increase the rate
rides such as pectin and carboxymethylcellulose increase viscos- of permeation of aromatic compounds (Brody 2002). However,
ity and consequently decrease absorption. Disaccharides such as even at 100% RH, EVOH outperforms LDPE as a barrier to organic
lactose and saccharose increase absorption, probably by a “salt- vapors (Carballo and others 2005).
ing out” effect of less nonpolar flavor compounds.
Selective flavor sorption by packaging materials constitutes a Storage conditions
major problem in beverages packaged in PE that has very high Generally, permeability, diffusion, and solubility coefficients
affinity for nonpolar compounds. Since most beverages are wa- follow a van’t Hoff-Arrhenius relationship, resulting in increased
ter based, the compounds more miscible in PE are absorbed. permeation with an increase in temperature (Brody 2002). Since
It is hypothesized that by lowering the solution polarity or cre- the effect is accentuated at ambient temperatures compared to
ating nonpolar regions (emulsified oil droplets) the equilibrium refrigerated temperatures, the adverse effects have appeared more
partition coefficient could be reduced thereby increasing flavor frequently in foods contained in retort pouches, aseptic packages,
retention. A study to determine whether oil or sucrose in solution and hot-filled flexible packages.
could reduce flavor sorption by PE showed that the sorption and The increased flavor absorption at higher temperatures is due
partition coefficient of various compounds into PE were greatly to increased mobility of the flavor molecules: changes in the poly-
influenced by the presence of oil in solution, but not sucrose. For mer configuration such as swelling or decrease of crystallinity and
compounds most preferentially absorbed by PE, addition of oil changes in the volatile solubility in the aqueous phase (Gremli
greatly reduced flavor loss, the reduction magnitude being very 1996). In 1 study, the total amount of flavor absorbed increased
significant with only 0.1% oil. It is postulated that flavors incorpo- considerably with temperature from 4 ◦ C to 40 ◦ C, the absorp-
rated into an oleoresin could be used to make beverages resistant tion by polyolefins such as LLDPE and OPP being several times
to flavor scalping (available from: www.foodproductdesign.com). higher than by the polyesters such as PC, PET, and PEN, indicat-
Durr and others (1981) reported a 50% loss of limonene from ing polyesters to be more preferable over polyolefins as packaging
orange juice to LDPE during 2 wk of storage. The sorption of materials (Willige and others 2002b).
limonene by LDPE from model solutions was much greater than Storage temperature has been demonstrated to affect the degree
that from orange juice attributed to the presence of other con- of sorption of aromas by PE. Sorption of limonene and myrcene
stituents in the juice, which increased the solubility of limonene from commercial orange drink stored for 12 wk in PET bottles
in the aqueous phase (Manheim and others 1987). This suggests was found to be 3.40 and 9.90 μg of limonene/g PET and 0.11
that the tendency of a beverage to lose flavor might be overcome and 0.33 μg of myrcene/g PET at 4 ◦ C and 25 ◦ C, respectively.
by the addition of components to the beverage that would reduce The higher values at 25 ◦ C could be due to the greater mobility of
the transfer of the individual compounds to the polymer. the molecules or more swelling of the polymer generating more
space for incorporation of the dissolved molecules (Nielsen and
others 1992a; Gremli 1996). Similarly, the solubility coefficient
Relative humidity (RH) for aldehyde vapors in linear LDPE was maximal at 25 ◦ C, with
The presence of water vapor often accelerates the diffusion sorption being lower at both 5 ◦ C and 75 ◦ C (Leufven and Stollman
of gases and vapors in polymers with an affinity for water. The 1992). The sorption of aldehyde vapors by polyvinyl chloride
water diffuses into the film and acts like a plasticizer, opening the (PVC) also decreased as the temperature decreased. VanLune and
polymer structure to molecular transport. The solubility of ethyl others (1997) suggested that the crystallinity of PET decreased
Vol. 6, 2007—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 23
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
while free volume increased at higher temperatures resulting in The most extensively studied aroma compound with respect
molecules’ easier absorption. to its sorption by polymers is limonene. Limonene is an unsatu-
Tawfik and others (1998) demonstrated that PET stored for rated terpene hydrocarbon present in citrus flavors. It is a highly
15 d at 37 ◦ C in a model solution containing 320 ppm limonene nonpolar substance and has shown high affinity for many poly-
absorbed 7 times more limonene than when stored at 5 ◦ C, but meric packaging materials. It is a highly nonpolar substance with
4 times more after 45 d. It is concluded that the diffusion pro- high affinity for many polymeric packaging materials. A decrease
cess is temperature dependent as evidenced by the slower rate in limonene content in stored orange juice is attributed to its
at a lower temperature. Nonetheless, absorption of decanal and lipophilic nature and, hence, the ease of its diffusion into the poly-
myrcene by PET film was found to decrease on prolonged storage mer (Moshanos and Shaw 1989b). The absorption of caryophyl-
notably due to desorption from the polymer to the model solu- lene and copeane was lower than that of limonene while that
tion on degradation (Willige and others 2002b). With increasing of octyl acetate and sesquiterpenes was similar. For limonene
storage time and temperature, degradation of aldehydes such as in model solutions, the affinity onto the polymer is in this or-
octanol, decanal, and citral was also observed in orange juice der: LDPE > polyamide > polystyrene. Also, an increase in the
(Durr and others 1981; Moshanos and Shaw 1989a). thickness of the polymer film and, consequently, the mass of the
polymer available as sorbent increase the sorption of limonene
(Ikegami and others 1991; Pieper and others 1992). The sorp-
Examples of Specific Flavor Systems with Packaging tion of limonene by LDPE has been demonstrated to be bipha-
Materials sic, showing both adsorption and absorption (Halek and Luttman
1991). A study on the flavor absorption by LDPE, PC, and PET
Citrus flavors from model solutions containing 7 flavor compounds showed va-
Citrus flavors, which contribute to the flavor of orange juice, lencene to be almost completely absorbed by LDPE, followed to
have been the major subject of study with respect to flavor scalp- a lesser extent by decanal, hexyl acetate, octanol, and nonanone
ing for quite some time. Citrus components from cold-pressed (Willige van and others 2003). Fewer and less of the flavor com-
and terpeneless oils have been shown to be absorbed into vari- pounds were absorbed from the model solution by PC and PET.
ous polymers such as LDPE, HDPE, PP, and surlyn used in aseptic However, limonene was readily absorbed from the orange juice
packaging (Charara and others 1992). Citrus essential oils consist by LDPE, while myrcene, valencene, pinene, and decanal were
of terpenes, sesquiterpenes, oxygenated compounds, and non- absorbed in smaller quantities. Berlinet and others (2005) have
volatile components while terpeneless oil consists of a higher reported the evolution of aroma compounds from orange juice
concentration of oxygenated compounds and a very low con- made from concentrate and stored in glass, standard monolayer
centration of terpenes. polyethylene terephthalate (PET 1), multiplayer PET (PET 2), and
Table 5 shows the percent absorption of flavors from cold- plasma-treated PET (internal carbon coating) (PET 3) to be due to
pressed and terpeneless orange oil extracted from 4 polymers the high acidity of the matrix, implying acid-catalyzed reactions.
using cyclohexane. LDPE has the highest absorption value be- PET packaging materials and their corresponding oxygen perme-
cause of its large amorphous area and low crystallinity, the ab- ability were found to have no correlation with the loss of aroma
sorption and diffusion taking place in the amorphous area of the compounds.
polymer. Terpene hydrocarbons being lipophilic tend to diffuse The quality of juices asceptically packed in laminated car-
into the amorphous regions of the polymers. HDPE and PP ab- tons has been the subject of extensive research during the last
sorbed constituents to a lesser extent probably due to their higher decades (Marshall and others 1985; Moshanos and Shaw 1989a,
crystalline structure. About 70% of limonene was lost from cold- 1989b). In another study, 2 polyester/polyolefin adhesive lami-
pressed orange oil in contact with LDPE for 4 d, while only a 30% nates coated with a PVDC-PVC copolymer were surface-exposed
loss was observed from orange oil in contact with HDPE and PP. to lemon juice and a hot sauce product as well as to food sim-
Surlyn was shown to absorb flavor constituents moderately. ulant systems at 45 ◦ C (Schroeder and others 1990). Sorption of
flavor volatiles resulted in delamination of both laminates fol-
lowing exposure to the food products, d-limonene being iden-
Table 5 --- Percent absorption of components from cold- tified as the primary component sorbed by the laminates. The
pressed and terpeneless orange oil (Charara and others shelf life of aseptically filled orange and grape fruit juices has
1992) also been shown to be significantly shorter in laminated cartons
% absorption than in glass jars, one of the attributes being the absorption of
d-limonene by the PE-contacting surface (Manheim and others
Component LDPE HDPE PP Surlyn 1987). Orange juice packaged in “juice board,” paperboard sand-
wiched between 2 layers of LDPE has been shown to have a slight
Cold pressed
turpentine-like off-flavor owing to the absorption of limonene into
Limonene 68 30 28 53
the paperboard (available from: www.foodproductdesign.com).
Pyrene 58 21 20 49
The retention of aldehydes, ethyl butanoate, and other flavor
Myrcene 66 28 22 78
compounds in orange juice is reported to be significantly higher in
Terpeneless
PET than in HDPE and LDPE (Ayhan and others 2001). Commer-
Limonene 54 22 36 39
cially, most aseptically filled juices are packed in LDPE-laminated
Copaene 40 ND ND 17
carton packs such as Tetra Brik and Combibloc. Food industries
Caryophyllene 34 4 9 19
often correct the absorptive effect by adding excess flavors to the
Octylacetate 35 ND 13 21
food for keeping taste and flavor acceptable for consumers until
Undecanal 30 ND 12 14
the end of the product’s shelf life.
Dodecanal 22 7 9 16
While flavor absorption may be high enough to affect the
Decanal 18 6 6 11
sensory quality of a packaged food, only a few authors have
Perillaldehyde 10 ND ND 7
conducted sensory tests to go along with the analytical re-
Geranial 1 1 ND 1
sults (Kwapong and Hotchkiss 1987; Manheim and others 1987;
Linalool 3 <1 1 2
Sharma and others 1990). Durr and others (1981) showed that
24 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 6, 2007
Scalping of flavors in packaged foods . . .

the absorption of d-limonene up to 40% did not affect the sen- Molecular weight of the migrant
sory quality of orange juice during 3 mo of storage at 20 ◦ C. Migration is a term used to describe the process of mass transfer
They suggested that d-limonene contributed scarcely to the flavor from a food packaging material to its contents. If one reduces the
of orange juice. Moreover, they considered limonene absorption migration process to the diffusion in and from the plastics, then the
even as an advantage, since limonene is known as a precursor migratability of plastic constituents corresponds predominantly
to off-flavor compounds. They also reported the storage temper- to the volatility or molecular weight of these organic substances
ature to be the main quality parameter for the shelf life of orange and to the basic diffusivity of a polymeric type (Franz 2000). For a
juice. given plastic, this means that the mobility of a migrant decreases
with increasing molecular weight.
Apple aroma compounds
Evaluation of 5 polymer packaging films with respect to the Solubility of the migrant in the food matrix
sorption of 10 apple aroma compounds from its aqueous so- Thermodynamic properties such as polarity and solubility in-
lution showed major differences in the amount of aroma com- fluence the migration rate due to interactions between polymer,
pounds absorbed by the polymers (Nielsen and others 1992b). migrant, and food stimulant (Helmroth and others 2002). For in-
LDPE, LLDPE, and PP absorbed larger quantities of aroma com- stance, if a migrant has poor solubility in the food simulant, it
pounds than did the polar polymers. PP absorbed larger amounts will rather remain in the polymer than migrate into the food sim-
of aroma compounds than the 2 polyethylenes, which may be ulant. This is often the case with nonpolar additives in nonpolar
a consequence of differences in crystallinity and morphology of polymers such as LDPE, PP, and PS in contact with more polar
the polymers. LDPE is reported to possess long-chain branch- food simulants such as water or 3% acetic acid. Higher migration
ing while LLDPE exhibits short-chain branching, but similar den- rates are, therefore, often found for fatty simulants such as olive
sity and equal heat of fusion and degree of crystallinity. Kon- oil, 95% ethanol, or isooctane than for aqueous food simulants
czal and others (1992) reported larger amounts of apple aro- (Till and others 1987; Riquet and Feigenbaum 1997; Linssen and
mas to be sorbed by LDPE than by EVOH with high ethylene others 1998). If the food simulant itself has a high affinity for the
content. polymer, then it may be absorbed by the polymer.
Most of the plastic constituents have a lipophilic rather than
Migration from Packaging Materials hydrophilic character and, therefore, migration increases strongly
Migration is an important safety aspect to be considered when with increasing fat content and especially so where the fat or oil
designing food packaging materials. Plastic additives, frequently represents the outer phase of the food matrix (Franz and others
used to improve polymer properties, and residual monomers or 2000). The increase in migration is not necessarily due to an in-
oligomers are not chemically bound to the polymer molecules crease in the substance’s diffusion coefficient due to interactions
and can, therefore, move freely within the polymer matrix. Conse- between the fat and the plastic as is often assumed (Baner and
quently, at the interface between the packaging material and food others 1992). The amount of substances migrating from plastics
they can dissolve in the food product and thus adversely affect into foodstuffs with high fat content is higher than in foodstuffs
the flavor and acceptability of the food (Hernandez and Gavara with water content owing to the higher solubility of the migrating
1999). Some of the additives that are more likely to migrate are organic compounds in fat compared to water. In fact, the higher
the plasticizers used in a range of plastics, but more particularly the fat content of the product, the higher the taste threshold con-
in PVC films where they can migrate in PVC food-contact sit- centration. For styrene, Bruck and Hammerschmidt (1977) devel-
uations (available from: www.foodscience.afisc.csiro.au). While oped an equation that relates the fat content of the food product
paper and board materials may transmit taint or odor to a food, to the taste threshold concentration as threshold (mg/L) = 0.0025
plastics have a much greater potential to do this. The presence (80 × % fat in food + % water in food). Conversely, water and
of monomers can contribute to significant off-flavors, styrene products with high water content (juices, skim milk) have lower
monomers at 0.5% in polystyrene (PS) being responsible for the taste thresholds usually on the order of 50 ppm.
characteristic plastic odor of many packaged foods. Fats and
oils in food products, however, can help mask off-flavors from Storage temperature
monomers and odorous residues from plastic processing. Never- At lower temperatures, including refrigeration, migration of
theless, as consumers shift toward lower fat products, off-flavors plastic components to foods may occur, the migration being
contributing directly via packaging materials may become more much slower than at higher temperatures (available at: http:/www.
of a problem. A number of components of ink may cause unpleas- foodscience.afisc.csiro.au).
ant flavors in food if the manufacture of the packaging material is An understanding of the interactions between food ingredients
not carefully controlled. Solvents associated with packaging inks and polymeric packaging materials requires knowledge of several
and with resins used in bonding the various layers of laminated factors. It is worthwhile to examine the relative balance of the
packaging films can be absorbed by the product to contribute various factors and their overall effect on migration.
off-flavors (available from: www.foodprodcutdesign.com).
The nature and strength of off-odors migrating to the food
depend on a number of factors, including the chemical nature Resins as a source of off-flavors
of the migrant (its volatility and polarity), the lipophilicity of Resins used in bonding of paper layers can be a culprit in
the food matrix, the physical structure of the food (solid com- the migration of off-flavors in packaged foods. Quaker Oats Co.
pared with liquid), time/temperature conditions during storage, discovered a piney/spruce off-flavor in packaged ready-to-eat
and the aroma activity (strength) of the migrant (available from: cereals (available from: www.foodproductdesign.com) that con-
www.foodproductdesign.com). Migration of off-flavors from the tributed an uncharacteristic flavor note to the cereal. When the
packaging material could be a result of plasticizers, inks, and packaging material used for the outer boxes was examined, it did
dyes used for graphics or from resins used in the bonding of the not possess a piney odor, but the inner glassine liner contained
package. a strong piney odor. The liner was composed of 2 sheets of Kraft
Some factors that could affect migration or be a source of unde- paper laminated with a resin in microcrystalline wax and over-
sirable flavors in the final packaged product are described briefly. waxed on both sides with paraffin wax.
Vol. 6, 2007—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 25
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
Odors from inks and dyes simulation under practical migration conditions (O’Neill and
Residual solvents from inks and dyes used for packaging Tuohy 1994). Styrene migration was found to depend strongly
graphics can cause off-flavor problems in foods (available from: upon the fat content of the milk and on the ethanol concentration
www.foodprodcutdesign.com). A nondairy coffee creamer manu- in the simulant. Pure water gave migration values considerably
facturer noticed shipping boxes of foil-wrapped nondairy creamer lower than all of the 3 samples of milk and 50% ethanol was
to have a severe musty odor. Results showed that all of the new shown to correlate approximately with 3.5% fat milk. Styrene
production samples contained the odor problem and had a peak migration from PS cups into different food systems such as wa-
identified as 1,3,5-trimethylbenzene (mesitylene). The trimethyl- ter, milk (0.5%, 1.55%, or 3.6% fat), cold beverages (apple juice,
benzene peak had a strong musty odor identical to the odor of orange juice, carbonated water, cola, beer, and chocolate drink),
contaminated boxes. Further checking revealed that the packag- hot beverages (tea, coffee, chocolate, and soup with 0%, 0.5%,
ing supplier had used a new type of ink containing high levels of 1%, 2%, or 3.6% fat), take-out foods (yogurt, jelly, pudding, and
1,3,5-trimethylbenzene for graphics on the foil packets. ice cream), aqueous food simulants (3% acetic acid, 15%, 50%,
Inks and model ink components incorporated deliberately into or 100% ethanol), and olive oil was also found to be fat depen-
carton boards at low temperature and during microwave heating dent, the maximum migration being for the fatty foods (Tawfik and
have shown benzophenone to migrate to the packaged food even Huyghebaert 1998). Studies of styrene migration from PS foam ar-
from PE-coated boards, attributed mainly to the permeability of ticles have shown the amount of styrene migrating into food oil to
PE to low-molecular-weight substances (Johns and others 2000). be proportional to the square root of the time of exposure (Lickly
Migration of benzophenone, benzylbutyl phthalate, butyl ben- and others 1995).
zoate, chlorodecane, and dimethyl phthalate was also detected
after storing the food at –20 ◦ C for 1 wk in the impregnated carton- Cork taint in wines
board. It was concluded that for inks used to print food-contact One of the most critical problems in the enological industry
materials, the content of low-molecular-weight volatiles should is associated with cork taint. Significant research has been car-
be controlled to lower the migration levels. ried out with respect to cork taint, particularly in wines. The main
compounds responsible for this off-flavor are some chloroanisoles
Off-odors from polyamide/ionomer laminates such as 2,4,6-trichloroanisole (TCA), 2,3,4,6-tetrachloroanisole
An off-odor with a smell of cat urine is reported to have oc- (TECA), and pentachloroanisole (PCA). Tests have confirmed the
curred in cooked ham products packed in polyamide/ionomer presence of 2,4,6-TCA and 2,3,4,6-tetrachlorophenol with ex-
laminate films (Piringer and Ruter 2000). A gas chromatograph tremely low-flavor thresholds, the dominant odor being close to
(GC) study of such products was able to identify the presence of that of mold (or moldy cork), leaving a sensation of dryness in
diacetone alcohol (DAA), which was used in the printing ink of the mouth very similar to the feeling of a plastic film covering the
the film that subsequently migrated into the laminate. Dehydra- taste buds (Cantagrel and Vidal 1990). Thus, use of compounds
tion reaction of DAA by the ethylene ionomer resulted in the containing chlorine in bad conditions in the steps in the manu-
formation of 4-methyl-4-mercaptopentane-2-one off-odor. It is facture of cork (or in the wine-making process) runs the risk of
proposed that when printing ionomer films or laminates contain- imparting an off-flavor.
ing ionomer in which foods with sulfur-containing proteins are
packed, the absence of mesityloxide and its chemical precursors Off-odors in premiums
such as acetone and diacetone alcohol must be guaranteed. A common promotional tool is the insertion of premiums in-
side food packages. The volatiles in the inserts, if not properly
Styrene taint in dairy products controlled, can impart an undesirable flavor to packaged foods.
An example of a product that has had styrene taint problems Odor testing of unwrapped premiums intended to be inserted in
over the years has been dairy products such as coffee cream- packaged dry mix beverages demonstrated a very strong “solvent-
ers and condensed milk packed in thermoformed PS single-serve like,” objectionable odor (Apostolopoulos 1998). The source of
portion-pack containers, the sensory threshold being on the order the residual chemicals was found to be solvents used with either
of 0.1 mg/kg (ppm) of styrene in the product (Baner 2000b). The the resin or the paint employed in the manufacturing and painting
British Ministry of Agriculture Foods and Fisheries (MAFF 1994) of the premiums. Overwrap films are recommended to prevent
carried out a trade survey of 22 coffee creamer portion packs and direct contact and contamination of the food products.
found styrene monomer levels in the product ranging from 23
to 223 μg/kg (ppb) with an average of 134 μg/kg. Of the com- Influence of Food Processing on Scalping of Flavors
monly PS-containing portion-pack materials, mono-material PS
was found to have the greatest migration followed by PS/PE; and Sorption
the material with the lowest migration was PS/EVOH/PE. Surpris- High-pressure food processing. Single-layer and multilayer
ingly, even the product packed in PS/EVOH/PE barrier material plastic structures can be used in combination with high-pressure
contained styrene at a perceptibly significant level at the end of processing (HPP) without concern that the process will enhance
the shelf life despite the EVOH barrier layer between the PS layer sorption. In 1 study, sorption behavior and flavor scalping po-
and the product. The possible explanation for styrene in the prod- tential of selected packaging films in contact with food simu-
uct comes from the fact that styrene from the PS layer transfers to lant liquids (FSL) (ethanol and acetic acid solutions) were evalu-
the inner PE layer during shipment and storage. This takes only ated after high-pressure processing (Caner and others 2004). HPP
a few days given the relatively high diffusion coefficient of PS treatment (800 MPa, 10 min, 60 ◦ C) showed d-limonene con-
and PE. However, lower temperatures and shorter shelf life can centration in the films and food simulants to be insignificantly
reduce the amount of styrene transferred to the product. affected by HPP, except for the metallized PET/EVA/LLDPE in
Measurement of styrene monomer migration from PS cups into comparison to the control pouches, which were exposed to at-
milk samples containing 0.5%, 3.5%, or 10% fat, as well as 4 wa- mospheric pressure at 60 ◦ C for 10 min in an electric oven.
ter/ethanol mixtures containing 0%, 15%, 50%, or 100% ethanol, Irradiation. Recently, irradiation has been explored as a viable
indicated that water, the simulant prescribed for milk under Eu- means in the shelf life extension of many foods. Apple cider pack-
ropean Commission legislation (Directive 85/572/EEC), does not aged in 3 plastic polymers, PS, LDPE, or nylon-6 (N6), and irra-
exhibit the required physicochemical properties for an adequate diated at 2 kGy was compared with unirradiated cider packaged
26 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 6, 2007
Scalping of flavors in packaged foods . . .

in glass containers (Crook and Boylston 2004). The extent of fla- 8 kGy (Buchalla and others 1993). However, irradiation of these
vor absorption by the packaging materials was influenced by the polymers can result in the release of hydrogen, CO 2 , CO, and
polarity of the polymer and the flavor compound, with plastic methane gases and the formation of volatile oxidation prod-
polymer having a greater affinity for compounds with similar po- ucts, including peroxides, alcohols, aldehydes, ketones, and car-
larity. Cider irradiated and stored in PS containers was shown to boxylic acids. Flexible food packaging materials (LDPE, EVAc,
have a lower rate of loss than untreated cider or irradiated cider PET/P/EVOH/PE) irradiated with low (5 kGy, corresponding to
packaged in LDPE for volatile flavor compounds characteristic of cold sterilization), intermediate (20 kGy), and high (100 kGy)
the apple or fruity taste and aroma. doses produced these volatile compounds in amounts that in-
creased with increasing irradiation dose (Riganakos and others
Migration 1998). The extent of radiation-induced changes depends on many
Microwave treatment. In the microwave oven, plastic contain- factors such as the type of polymer, processing exposure, and
ers and wraps are often warmed to a point that plasticizers are irradiation conditions (Buchalla and others 1993). Odor inten-
released from the plastic into the food (Bishop and Dye 1982). sity values for various polymers have been reported by Tripp
Numerous studies indicate that some plasticizers can cause un- (1959). More intense odors on irradiation were observed in LDPE
desirable side effects in animal tissue, and that the amount of than in HDPE, developing stronger off-odors than PS and vari-
migration could be as high as 23% of the total weight. In 1 study, ous polyamides and polyesters. The intensity of off-odors of ir-
migration of plasticizers such as dioctyladipate (DOA) from plas- radiated PE was found to increase with oxygen concentration
ticized PVC and acetyltributylcitrate (ATBC) from polyvinylidene in the atmosphere with a good correlation existing between the
chloride (PVDC/PVC) (SaranTM ) films into ground meat heated for amount of products formed by irradiation and the intensity of
4 min was found to be 84 mg/kg (14.7 mg/dm2 ) and 95.1 mg/kg off-odor (Azuma and others 1984). The odor-producing volatiles
(2.5 mg/dm2 ), respectively (Badeka and Kontominas 1998). Such from LDPE films irradiated with a dose of 20 kGy from a 2.5 MeV
migrations could result in deterioration of the final food quality, electron beam were identified to be mainly aliphatic hydrocar-
posing off-flavor and/or safety problems. The migration of com- bons, aldehydes, ketones, and carboxylic acids.
pounds from a polymeric material into a food-contacting phase Migration studies with 9 different polymers irradiated at 60 kGy
would depend on several factors such as the nature and thick- showed increased migration into distilled water for polyamide-6,
ness of the packaging material, the nature of the food in contact, polyamide-11, polyvinyl chloride-vinyl acetate, and poly (vinyli-
initial concentration of additives in the polymer, compatibility of dene chloride-vinyl chloride) after γ -irradiation (Killoran 1972).
the additive/polymer system, temperature, time of contact, and The extracted substances were identified as low-molecular-
others. weight materials of the polymers and, in the case of PVC, as an
One development in food packaging that has received much ester-type plasticizer. Transfer of off-odors from 2 laminates (with
attention lately is the microwave susceptor, a package devel- LDPE and HDPE as inner layers) into water was evident at the low-
oped to meet consumer demands for convenience and qual- est dose applied (10 kGy) and increased with the absorbed dose
ity in microwaveable food products. A susceptor is typically to reach a maximum at 150 kGy; however, during storage, the off-
a piece of polyester film that has been metallized with alu- odors gradually disappeared. Nevertheless, polyester-aluminum-
minum laminated either to paperboard or between 2 layers of HDPE did not produce any off-odors up to 500 kGy.
paper. Food/package interactions that result from the use of Retorted foods. Migration from multilayer laminated film
microwave susceptors and dual ovenable trays have been ex- pouches intended for retort foods was investigated using HPLC
tensively studied by the U.S. Food and Drug Administration analysis, a fluorescence detector, and measurements of residue on
(FDA) ’s Indirect Additives Laboratory. Susceptors are typically evaporation, consumption of potassium permanganate, and total
constructed of plastic such as PET, adhesives, and paper, and organic C (Uematsu and others 2005). HPLC analysis revealed
temperatures in excess of 212 ◦ F are common for such pack- that the levels of migrants in oil and water heated in the pouches
aging. At elevated temperatures, both volatile and nonvolatile (121 ◦ C, 30 min) were 10 times those in the corresponding official
chemicals from the package can migrate into foods (Hollifield simulants, n-heptane (25 ◦ C, 60 min), and water (95 ◦ C, 30 min).
1991). Generally, the more paper in the susceptor construction, Bisphenol A diglycidyl ether and related compounds were found
the greater the amount and number of volatile substances re- in oil and water heated in the pouches, as well as in the official
leased on heating. The number of substances released at lev- simulants. Results indicate that these compounds were present in
els greater than 0.5 μg/inch2 of susceptor surface from suscep- the adhesive between the laminated films and migrated through
tors containing acrylic-based or vinyl-acetate-based adhesives the food-contact film of the package.
includes acetone, methyl vinyl ketone, pentanal, toluene, hex-
anal, furfural, heptanal, benzaldehyde, nonanal, furan, isobu- Analytical Techniques
tanol, acetic acid, butanol, octanal, styrene, octyl acetate,
5-hydroxymethylfurfural, and crotonaldehyde (Hollifield 1991). Sorption of food flavors
Ionizing radiation. Irradiation for the control and reduction of In the quantitative analysis of flavor sorption by packaging
microorganisms and insects and the extension of product shelf life materials, solvent extraction of flavor compounds is generally
has become a potential preservation technique in many countries. followed by determination of the extract concentration by GC
Several researchers have studied migration into food simulants, (Imai and others 1990). Increasing the extract concentration by
describing it to be a consequence of irradiation. Lox and others distillation or vacuum evaporation is usually used to increase
(1991) found an increase in migration as a function of dose up the sensitivity of measuring low-magnitude sorption (Kwapong
to 10 kGy and a decrease at higher doses from extruded PVC and Hotchkiss 1987). Solvent extraction and multiple headspace
irradiated with 3 to 25 kGy γ -rays. With accelerated electrons, the extraction using a purge and trap injector (MHE-PTI) can also
migration increased steadily with the absorbed dose. However, no be used to study sorption. While the solvent extraction step is
significant migration was observed with LDPE and PP at absorbed highly tedious and time consuming, the MHE-PTI is more con-
doses of up to 25 kGy with either electron irradiation or a cobalt- venient, rapid, fully automated, and suitable for volatile aroma
60 γ -source (Rojas and Pascat 1990). compounds.
The gas permeability of LDPE, HDPE, PET, and PVC pack- The techniques currently employed in the evaluation of flavor
aging materials is unaffected by irradiation doses of up to sorption include GC-MS (mass spectroscopy) analysis using static
Vol. 6, 2007—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 27
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
headspace sampling, dynamic headspace sampling, and solid- a possibility that the bottles returning to the loop could have
phase microextraction (SPME) (available from: www.foodprodu- been used for the storage of detergents, pesticides, and other
ctdesign.com, Paik 1992); solvent extraction coupled with chemicals, posing a threat of severe contamination problems
GC (Shimoda and others 1988; Imai and others 1990; (Demertzis and Franz 1998). A quick test to predict the sorption
Nielsen and others 1992a); electronic nose (available from: properties of refillable bottles involves measuring the uptake of
www.foodproductdesign.com), supercritical fluid extraction (SFE) model contaminants onto bottle strips and subsequent remigra-
coupled with GC (Nielsen and others 1991; Johansson and oth- tion of the chemicals in food simulants. The model contaminants
ers 1993); and vacuum microgravimetry (Roland and Hotchkiss include alcohol-type compounds such as ethylene glycol, phe-
1991). nol, n-hexanol, 2-phenylethanol, menthol, and 1,2-decanediol;
A novel method developed by Nielsen and others (1991) using ester/ketone-type compounds such as ethyl acetate, cyclohex-
supercritical carbon dioxide extraction directly coupled to GC anone, iso-amyl acetate, benzopheneone, linalyl acetate, and
might prove essential in the continuous investigation of absorbed methyl stearate; hydrocarbon-type compounds such as toluene,
food components in plastic packaging materials. It is based on the n-heptane, p-xylene, limonene, phenyl cyclohexane, and phenyl
advantageous properties that carbon dioxide has at a pressure and decane; and chlorinated compounds such as chlorobenzene and
temperature above the critical point when the carbon dioxide is 1,1,1-trichloroethane. The GC analytical methodology is usually
in the supercritical stage. Leufvén and Hermansson (1994) used applied in the detection of the contaminants.
SFE with carbon dioxide to extract aromas from film samples and In the headspace solid phase microextraction (HS-SPME),
deposit them in a chemical adsorbent for thermal desorption onto volatiles are captured by SPME based on the theory of equilibrium
a GC-FID (flame ionization detection) capillary column. Nielsen partitioning of the analytes between the solid phase of SPME, liq-
and Jägerstad (1994) also used SFE to strip the polymer off the uid or solid sample matrix, and headspace above the matrix and
sorbed volatiles, which was then deposited directly onto a GC- analyzed by GC (Zhang and Pawliszyn 1993). Traditional meth-
FID capillary column for elution. These SFE techniques are limited ods for the extraction and concentration of volatile compounds
to aromas that are soluble in the given supercritical fluid (Nielsen for analysis by GC such as liquid-liquid extraction, solid phase ex-
and others 1991). traction, SFE, static headspace sampling, or dynamic headspace
In a study on the interaction of orange juice with inner pack- (purge-and-trap) methods have one or more drawbacks such as
aging material of an aseptic product, the volatile components ab- high cost, multistep preparation, low sensitivity, prolonged ex-
sorbed by the inner packaging material were extracted by ether traction time, artifact formation, or solvent contamination (Brag-
and analyzed by GC-MS (Jeng and others 1991). The empty pack, gins and others 1999). Compared to these methods, the SPME
after rinsing with deionized water and air-drying, was filled with technique is a simple, rapid, and economical method requiring
ethyl ether for 24 h at room temperature and the ethyl ether ex- no solvents (Yang and Peppard, 1994). Nevertheless, SPME anal-
tract so obtained was concentrated with a vigreux column. Ethyl ysis is reported to be affected by factors such as the nature of the
cinnamate was added as an internal standard. The volatile com- SPME solid phase, adsorption time, adsorption temperature, salt
ponents so extracted from the inner packaging material were sub- addition, stirring condition, and sample size (Steenson and oth-
jected to GC analysis on a Varian 3400 gas chromatograph using ers 2002; Lee and others 2003; Rodriguez-Bencomo and others
a fused silica column with a stationary phase equivalent to Car- 2003).
bowax 20 M. In another study, using headspace chromatography, The oxygen electrode (OE) method provides a rapid and accu-
attempts were made to “fingerprint” key flavor compounds sorbed rate test for gauging the absorption of volatile compounds. In a
by aseptic packages containing juice products (Arora and others study to measure scalping of limonene by LDPE, the LDPE test
1991). The package that contained juice showed extra peaks in film was mounted on a YSI 5331 OE. The probe was then placed
the chromatogram compared to the control container, which did in the headspace of a flask that contained the selected volatile
not contain any juice. The extra peaks represented the uptake of at the test temperature (Sadler and Braddock 1991). Absorption-
flavor compounds by the package. induced changes in the readings were monitored on a strip chart
In a study on the sorption of 5 classes of flavor compounds recorder. When stable permeation readings indicated maximum
(aldehydes, methyl ketones, methyl esters, alkylpyrazines, and absorption, the probe was withdrawn and placed in an air stream
sulfur compounds) representing a wide range of food products equilibrated to the test temperature. As the air stream forced
such as dairy, fruit, vegetable, and meat products by PP at room desorption of limonene from the probe membrane, a strip chart
temperature, the PP was cut into small discs and mounted onto a recorder was used to monitor permeability loss in response to des-
silanized stainless steel wire alternating with silanized glass beads orption. Desorption was monitored until the permeation reading
(Arora and others 1991). The stainless steel wire with PP discs and was within 5% of its reading prior to volatile treatment. Limonene
glass beads were inserted into a silanized screw tight glass bottle. absorption produced an increase in oxygen permeability, which
Each of the glass bottles containing a 2% alcoholic buffer of simu- appeared to be proportional to limonene concentration. Time-
lated milk ultrafiltrate (SMUF) and a flavor compound was placed course changes in the readings were used to calculate diffusion
on a shaker for uniform dispersal of the flavor compound for 24 h coefficients of volatiles in the polymer. Diffusion coefficients were
at room temperature (24 ◦ C). Two sets of controls (buffer solution found to be proportional to the volatile’s solubility in the polymer.
containing only the flavor compound and buffer solution contain- A vacuum-gravimetric method to quantify the sorption of
ing the flavor compound, wire, and glass beads) were placed on aroma compounds by food-contact polymers developed by
the shaker along with the bottles containing the PP samples. After Roland and Hotchkiss (1991) consisted of a microgravimetric
24 h, the flavor compound in the buffer solution was extracted balance contained in a vacuum chamber. Polymer samples were
with methylene chloride and analyzed by GC. The GC analysis placed on the balance in a sealed chamber and outgassed to 10−4
was performed using a Supelcowax 10 fused silica capillary col- torr. Small amounts of aroma compounds (d-limonene or linalool)
umn. The buffer solution in the controls was also extracted in were admitted to the evacuated chamber and the mass increase in
the same manner as the buffer solution containing the PP discs. the polymer resulting from compound sorption and the pressure
The quantity of flavor compound extracted was determined using within the vessel were recorded by means of a computer. This
peak areas. Calibration curves were generated using peak areas method is proposed to be a useful predictor of individual flavor–
from known concentrations of flavor compounds. polymer interactions at flavor concentrations and amounts that
In the use of refillable bottles such as PET and PC, there is are usually encountered in foods.
28 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 6, 2007
Scalping of flavors in packaged foods . . .

In a method based on weight change in order to study the ab- technique is very suitable for the analysis; it has been used in
sorption of citrus flavor volatiles by LDPE, tarred LDPE sheets the EU project Specific Migration by heating the PS dissolved
were stored in a closed desiccator over a 50-mL pool of the in dimethylacetamide at 90 ◦ C for 120 min. If the migrant is a
selected volatile (Sadler and Braddock 1991). After 1 wk, the nonvolatile compound it is essential to use a liquid extraction
samples were removed, weighed, and desorbed in a forced-air step. The solvent used should both dissolve the target compound
stream. Weight loss was recorded every 15 min until the poly- and also swell or dissolve the polymer matrix. When the polymer
mer was within 5% of its weight prior to volatile treatment. The is dissolved in a solvent, the polymer is then usually reprecip-
solubility of the volatile in the polymer was calculated as: itated by addition of a solvent in which the polymer is insolu-
ble.
(A − B)/B × 100 Usually, extraction procedures are carried out with hand shak-
ing (Garcia and others 2006). Nevertheless, sometimes ultrason-
where B and A represented the polymer weights before and after ics (Marque and others 1998) or maceration (Monteiro and others
volatile absorption. 1998) could be employed to improve the process. Gramshaw and
Cava and others (2005) analyzed the diffusion behavior of Vandenburg (1995) used dynamic headspace to extract styrene
limonene in LDPE as a function of sample thickness, perme- from thermoset polyester passing through the U-tube nitrogen at
ant concentration, and the outer medium by transmission Fourier 25 mL/min and heating the oven at 200 ◦ C. To analyze styrene
transform infrared (FT-IR) spectroscopy. A surprising reduction in dimers and trimers, Soxhlet extraction with dichloromethane was
diffusion (D) and permeability (P) coefficients with reducing film used, followed by size exclusion chromatography to clean up the
thickness was observed, most likely attributed to the morpholog- dichloromethane extracts.
ical differences arising during cast film extrusion. Moreover, the Chromatographic separations in the gas and liquid phases are
limonene desorption kinetics were found to slow down consid- currently state of the art (Brandsch and others 2000). In the au-
erably when desorption of the volatile was carried out in water tomatic PTI coupled to a GC used for the dynamic MHE of
compared to desorption in air. Finally, the sorption kinetics of volatile compounds from aqueous solutions as well as films,
limonene in LDPE were found to be much slower when the poly- trapped volatiles after the purge time are thermally flash des-
mer was put in contact with pressed orange juice (similar to a real orbed and directly injected onto the GC column (Feigenbaum
juice packaging case) than when it was put in contact with the and others 1998). In 1 study, the source of an off-odor in pre-
pure volatile. A remarkable finding arising from this work is that miums intended for use with dry mix beverages was evaluated
the diffusion coefficient of limonene in LDPE can vary by up to 2 in accordance with the ASTM F 151-86 (ASTM 1986) method
orders of magnitude depending on the testing conditions, mainly using headspace GC/mass spectrometry (Apostolopoulos 1998).
limonene concentration but also polymer morphology, and, con- The premiums were placed in Mason jars which were sealed with
sequently, these observations may well account for the extensive TeflonTM -lined lids, equipped with sampling ports. The Mason jars
variability reported for this permeant in the existing literature. containing the premium samples were placed inside a mechani-
cally convected oven and heated at 110 ◦ C for 90 min to ensure
Migrants from packaging materials vaporization of the premium residuals into the headspace of the
With regard to migration, the control of transfer from plastic Mason jars. Using a preheated gas-tight syringe to avoid conden-
packaging materials into foods is based on the measurement of sation of the volatiles, headspace aliquots of 1 mL were with-
the substance in the food or simulant. The direct migration mea- drawn from the Mason jars and injected into GC-MS, equipped
surement consists of measuring either directly in foodstuffs or with a CP-Sil 8 CB chromatographic column operated at 20 ◦ C for
more commonly mimicking as closely as possible a given food 2 min and then increased at 10 ◦ C/min to 250 ◦ C. The compounds
packaging application using food simulants. The semi-direct mi- present in the injected aliquots were separated in GC-MS scans
gration test applies more severe test conditions by using volatile with mass spectral identifications. GC-MS was also used in the
solvents with strong interactions toward the plastic to enhance the identification of volatiles produced during electron beam irradia-
migration rate from the plastic. Thus, the extraction test is based tion (Riganakos and others 1998). About 1.2 to 1.6 g of packaging
on accelerated mass transport mechanisms where the diffusion materials was weighed into glass headspace vials, sealed, and ir-
coefficients of migrants are increased by several orders of magni- radiated. Helium gas at a flow rate of 30 mL/min was passed for
tude compared to the original migration test. As a rule, extraction 20 min through the headspace vials maintained at 80 ◦ C. The
tests are designed such that they make use of the following prin- volatile compounds were collected on a Tenax GC plug filled
ciple: polar polymer + polar migrant + polar solvent = worst into the glass liner of an Optic PTV-Injector.
case = nonpolar polymer + nonpolar migrant + nonpolar sol- The headspace gas chromatographic (HSGC) method for deter-
vent (Franz and others 2000). mining volatile substances emitted from high-temperature food
When an off-odor problem occurs and is suspected to be pack- packaging is used to screen microwave susceptors and fatty food
aging related, it is suggested that the packaging supplier be ap- simulants (McNeal 2000). Levels of butadiene in a food or food
proached to find out the nonproprietary aspects of the compo- simulant are usually determined by HSGC with automated sam-
nents used during manufacture. The next step is to obtain an ple injection and by FID (Franz and others 2000). HS-SPME cou-
analytical profile of the product, typically done using dynamic pled to GC-electron capture detection can be used for the direct
headspace GC-MS, while simultaneously conducting taste and determination of chloroanisoles in wine samples (Urunuela and
odor evaluation. To confirm that the off-flavor problem is indeed others 2004).
packaging related, a control should be run where the product Additional selective methods of considerable importance in-
is stored using a relatively inert barrier such as glass. Finally, clude direct mass spectrometry using an electro-spray-ionization
one needs to look for volatiles that correlate with the defect and (ESI) or atmospheric pressure ionization (API) ion source, which
find their threshold levels. If off-flavor increases over time, then can quickly provide data for several species migrating into a stim-
it would be best to look for alternative packaging materials or ulant in 1 run. The ESI-MS is especially well suited for complex
packaging materials with different barrier compositions. nitrogen-containing and phenolic structures; combinations of
In general, the first stage in the determination of the migrants HPLC with ESI-MS or AI-MS also provide a very powerful tool. An
in polymers is their separation from the matrix. When the mi- analytical procedure based on headspace GC and mass selective
grant is a volatile compound such as styrene, the headspace GC detection is usually used to determine volatiles whereas HPLC
Vol. 6, 2007—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 29
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
with UV detection is quite suitable for determining potential address concerns about whether the packaging will affect ap-
migrants of high molecular weight such as PET oligomers and pearance, flavor, odor, and other factors influencing consumer
acceptance. According to FDA regulations, any packaging mate-
adhesive plasticizers arbitrarily classified as nonvolatiles (Holli-
field 1991). rial that comes in contact with food must receive FDA clearance
Total migration of components from packaging materials into before it can be used (Buck and Bussey 2002). While consumer
acceptance issues will determine the success or failure of a given
fat-releasing foodstuffs is based on the determination of the weight
product, unsafe packaging is a public health issue and will af-
of a sample of the packaging material before and after its storage in
fect the future of the food and packaging manufacturers. Package
a test fat under standard conditions, a correction being applied for
component migration can result in food adulteration, which vi-
the residual fat retained in/on the sample (Figge and others 1978).
The latter may be determined by physical or chemical methods, olates government laws, and food safety professionals must be
the calculation being based in most cases on a single component aware of regulations pertaining to this area. The major purpose
for performing migration studies is to estimate exposure to food
of the triglyceride mixture that has migrated into the sample. With
packaging components (Begley 2000). Exposure is calculated to
most test fats, differential migration of the individual components
determine an estimate of daily intake (EDI). The EDI for a partic-
of the fat into and incomplete extraction of the absorbed fat from
ular migrant is compared with the acceptable daily intake (ADI)
the test polymer are serious sources of error. Fewer problems are
associated with the use of 14 C-labeled HB 307 as the fat simulant
of the migrant, as determined by FDA toxicologists.
suitable for all types of plastics, including the highly crosslinked
In addition to positive lists and SMLs, general provisions have
and insoluble types. been introduced under the European Community Directive con-
A reference material for the determination of overall migration
trolling the suitability of materials and articles on the basis
from a plastic coextrudate into the fatty food simulant olive oil
of overall migration limits. Also, European Council Directive
was produced and certified in an interlaboratory study (Lund and82/711/EEC, as amended by European Commission Directive
others 2000). The analyses were carried out according to the ENV93/8/CEE (European Commission 1993) establishes in Article 3
1186 standard from the European Committee for Standardization that “verification of compliance of migration into foodstuffs with
(CEN) with exposure of the coextrudate to olive oil for 10 d at the migration limits shall be carried out under the most extreme
40 ◦ C. After an initial preliminary interlaboratory study, 8 lab-
conditions of time and temperature foreseeable in actual use.”
oratories participated in the certification round, and 2 different
Time and temperature are 2 factors that affect the migration of sub-
methods were used to obtain single-sided exposure of the plas- stances from plastic materials, in addition to other factors such as
tic to the oil. A reference value of 8.6 mg/dm2 to 1.4 mg/dm2 compression, stacking, or vacuum packing that should be taken
(half width of the 95% confidence interval) was obtained, which into account when carrying out migration tests under the worst
is within the range relevant for the regulatory limit (10 mg/dm2 ),
foreseeable conditions. The transfer of substances is regulated by
making this reference material suitable for laboratories measuring
2002/72 with 2 different migration limits, that is, overall migra-
according to the EU overall migration limit. tion limit and SML. The overall migration limit, the total quantity
A neutron activation method developed for the analysis of of substances released by the sample, is 60 mg/kg or 10 mg/dm2 .
HDPE, LDPE, PP, PET, and PS food-contact plastics provides for Some substances are also regulated with SML, because toxico-
determination of over 50 elements at a concentration of be- logical data submitted to the Authority are limited or its impact
low 1 mg/kg (Thompson and others 1996). This technique has in higher transfer level is considered to be a concern. SMLs are
now been extended to study migration from food-contact mate- mentioned in Annex II of 2002/72/EC.
rials into standard food simulants (olive oil, acetic acid, ethanol,
The Plastic Materials and Articles in Contact with Food Regu-
and water). Samples of plastic are irradiated in a thermal neu- lations, 1998, set an overall migration limit for all food-contact
plastics, the limit being 10 mg/dm2 of plastic surface area, in
tron flux to produce radionuclides of the elements present in the
plastic. Over a period of time, the radionuclides of these ele- general. However, a limit of 60 mg/kg of food applies specifically
ments may travel from the plastic into the food simulants, and in the case of containers or similar receptacles with a capac-
hence migration can be determined. Gamma ray spectrometry ity between 0.5 L and 10 L, or which have a contact area that
cannot be determined, and for sealing devices such as caps, gas-
performed on the simulants at the end of the test is used to quan-
kets, and stoppers (available from: www.food.gov.uk). The Aus-
tify the migration, any activity being attributed to the migration
of radionuclides of elements in the plastic. Detection limits oftralian Food Standards Code has set maximum migration levels
about 0.002 mg/kg were achieved for antimony (Sb) in retail PET for 3 specific monomers, vinyl chloride, acrylonitrile, and vinyli-
bottles. dene chloride, because of their known potential toxicity (avail-
able from: www.foodscience.afisc.csiro.au).
It is imperative that every analytical method adopted for migra-
tion studies be capable of reaching the required detection limit, A packaging material with exceptional importance for foods
is PE. Depending on the source of this plastic, water in con-
typically 50 parts per billion or less (Buck and Bussey 2002). To
verify whether the methodology is capable of delivering the cor-tact with it can produce characteristic flavor changes. The de-
scription of the PE odor ranges from candle-like, stuffy, musty to
rect results, FCN (Food Contact Notification) rules state that each
analytical method be validated. Extracts of samples or controls soapy, to rancid. For this reason, PE used for food applications
must be spiked with the potential migrant at known levels and has high-quality standard requirements. Another packaging ma-
then analyzed using the same method applied to the sample ex- terial, for which toxicity and safety have been extensively studied
tracts. Adequate recovery of the spiked material shows that the is styrene, which is reported to have no health consequence at
method works as reported. While chemical analysis guides the the levels commonly found in foods. The current European legis-
lation sets no SMLs for styrene in food, which means its content
search for off-flavor contributors in a food, identifying these also
requires sensory evaluation tools. is controlled by the overall migration limit of 60 mg/kg in the
food. The overall migration limit is never reached because styrene
creates a strong astringent chemical plastic off-taste at levels
Legislation much lower than the 60 mg/kg. Recent surveys of styrene lev-
A major concern in packaging is whether the packaging com- els in foods by the MAFF in England have led to the conclusion
ponents will migrate into the food product. In addition to con- that there is no toxicological concern considering the levels (<1
cerns about the safety of a packaged food, packagers must also to 134 μg/kg) found in foods (MAFF 1994).
30 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 6, 2007
Scalping of flavors in packaged foods . . .

Approaches to the Reduction of the Scalping Process remove volatile food components may be an effective means
Judicious selection of polymers is the best way to reduce scalp- to remove unpleasant flavor notes since ketones and aldehy-
ing by the use of crystalline polymers, polymer blends, or edible des contain functional carbonyl groups that readily react with
films (Gallo and others 1999). Fluorination of polymer surface amines.
and inert coatings on the polymer surface is yet another approach.
Some of the common measures to prevent the scalping process, Choice of packaging material
thus maintaining the integrity of the packaged food items, are The choice of plasticizers must be made on the basis of the
described below. film’s end use. A possible approach to reduce the potential
for migration of plasticizers from PVC into foods is to replace
Flavor encapsulation monomeric with polymeric plasticizer compounds of higher
Protection mechanisms designed into commercial flavor de- molecular weight with reduced tendency for migration due to
livery systems provide for release of the flavor at the appropriate limited mobility in the polymer matrix, for example, a polyadipate
time. Advances in encapsulation technology allow encapsulation ester-type plasticizer used at 70% level for low-molecular-weight
of hydrophobic or hydrophilic flavors, which are available in a PVC or 50% level for a high-molecular-weight PVC (Demertzis
range of particle size, shape, and solubility. Flavors can be en- and others 1990).
capsulated to protect them from undesirable interactions with the Vinylidene chloride polymers. Vinylidene chloride polymers
components and the package. The industry is developing micro- are often used in connection with other structural polymers as
and macroencapsulation technologies utilizing various coatings a barrier to prevent the entry of oxygen into food containers and
such as polymers, waxes, fats, starch, hydrogenated vegetable to limit flavor scalping during long periods of storage. Although
oils, proteins, maltodextrins, mono- and diglycerides, gum ara- these polymers display outstanding characteristics for use in food
bic, alginates, gelatin, and cellulose compounds (available from: packaging, they suffer from sensitivity to thermal treatments, un-
www.foodproductdesign.com) dergoing heat-induced degradative dehydrochlorination at pro-
cess temperatures of 150 ± 170 ◦ C. To scavenge evolved hy-
Electron beam irradiation drogen chloride and thus prevent the formation of metal halides
Electron beam irradiation of ethylene vinyl acetate copolymer by interaction with extruder walls, these materials are usually
films is shown to markedly depress the sorption of flavor com- blended with a small amount of passive base prior to processing
pounds such as hydrocarbons and low-polarity compounds (Mat- (Howell and Uhl 2000).
sui and others 1990). This effect is attributed to the radical reac- Biobased food packages resistant to scalping. In general, plas-
tions evolving changes in the structural characteristics such as tic materials are not inert and where direct contact between the
crosslinking and scission reactions (Lawton and others 1960). packaged product and the plastic container occurs, there can be
migration of substances into the product. The amount of any com-
Selective scalping ponent that migrates into food depends on the original concentra-
Few researchers have addressed how scalping, particularly se- tion of the particular component in the polymer and its solubility
lective scalping, can improve the flavor profile of food systems. as well as the temperature, mechanical stresses, and contact time.
Polymer blends included with an agent that has an affinity for spe- Therefore, there is a considerable interest in replacing some or
cific compounds can be used to proactively remove deleterious all of the synthetic plastics by biodegradable materials in many
substances in a packaging environment (Del Nobile and others applications.
2002). Polylactic acid (PLA) has finally arrived as an alternative to
The possibility to trap degradation products (produced by PET, PVC, and cellulosics in some high-clarity packaging roles.
chemical reactions) with scavengers such as a zeolite additive PLA, an aliphatic polyester featuring high-clarity, gloss, stiffness,
or antioxidants and hence prevent degradation products from mi- and easy processing, is fabricated by polymerizing lactic acid
grating to the polymer film surface and further into food in contact monomer (LA) produced by carbohydrate fermentation of corn
with the film was investigated by Anderson and Forsgren (2005). dextrose. Currently, PLA is being used as a food packaging poly-
Adsorption of oxidative degradation products in a zeolite addi- mer for short-shelf-life products with common applications such
tive or protection of LDPE by using antioxidants could prevent as containers, drinking cups, sundae and salad cups, overwrap
off-flavor in the packed product, such as water. and lamination films, and blister packages (Ikada and Tsuji 2000).
The migration of low-molecular-weight compounds formed The novel resin is forging roles in thermoformed cups and con-
during polymerization, processing, and forming of packaging ma- tainers and also single-serve drink bottles. Synthesized from pro-
terials could be a problem. For example, acetaldehyde is formed cessed corn, a renewable plant feedstock, it biodegrades after
in the polyester PET by the thermal decomposition of the ethylene use, if composted. PLA synthesis requires 30% to 50% less fos-
glycol hydroxyl terminal group and the main chain of the poly- sil fuel than polymers synthesized from hydrocarbons and thus
mer (Ikgarashi and others 1989). In their study, poly (m-xylidene reduces carbon dioxide emission. These “green” benefits could
adipamide) (nylon MXD6), D-sorbitol, and α-cyclodextrin provide users with a marketing edge. Nonetheless, PLA faces hur-
aldehyde-scavenging agents were blended with poly (ethylene dles, including its high density (1.25 g/cc) relative to PP and PS.
terephthalate) and thermally pressed into films. The total amount It also has high polarity, making it difficult to adhere without tie-
of aldehydes sorbed by the films was 2 to 10 times higher layers to nonpolar PE and PP in multilayer structures. But the
for films containing the aldehyde-scavenging agents than non- greatest stumbling block is PLA’s cost, currently an average of
blended films. Aldehyde-scavenging films demonstrated selective $1.30/lb. Notably, PLA delivers a balance of properties that has
scalping, preferably for smaller-molecular-weight aldehydes. generated enthusiastic interest from some end users. A good ex-
Odor absorbent packaging can also be used in combination ample of PLA’s early success is a biaxially oriented PLA (BOPLA)
with base polymers such as PET, LDPE, and PP to eliminate off- film made by Mitsubishi Plastics in Japan. This BOPLA film is lam-
odors produced during long-term storage (Perchonok 2003). The inated to paperboard in a golf-ball package for Dunlop Japan.
odor-producing compounds targeted could be aldehydes and ke- The reverse-printed PLA film becomes the clear viewing win-
tones associated with lipid oxidation and cooked odors. Ketones dow when a panel is die-cut out of the paperboard. BOPLA film
are found in beverages and foods such as ultra-high tempera- laminates easily and justifies Dunlop’s “recyclable-compostable”
ture (UHT) milk. The use of polymeric amines in packaging to claims.
Vol. 6, 2007—COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY 31
CRFSFS: Comprehensive Reviews in Food Science and Food Safety
PLA and PHB (polyhydroxy butyrate) bottles or cups could be vent the problems usually associated with flavor scalping.
used for packaging fresh unpasteurized orange juice (Haugaard For juices. International Paper Co. (Memphis, Tenn., U.S.A.)
and Festersen 2000). PLA cups have relatively low water vapor has introduced a new generation of “Super-Marketing” beverage
permeability and high resistance to scalping compared to PE. packaging for juice and milk products, which helps lock in vi-
Since PHB has a much lower oxygen transmission rate than PLA tamins and retain flavor longer. International Paper’s patented
(Krochta and De Mulder-Johnston 1997) and PHB has high water Barrier-Pak (R) technology reduces flavor oil scalping by up to
resistance (Hanggi 1995), coating of PLA with PHB is expected to 20%, preserving the fresh taste of juice products.
give a useful biobased packaging material for beverages. Packag- The Lisle, Ill., based EVAL Co. of America recommends the
ing materials based on 100% PHB are also expected to be useful use of EVOH in direct contact with juices to reduce flavor/aroma
for beverages. migration (available from: www.foodproductdesign.com). EVOH
One major concern for biobased packaging materials is that provides an effective barrier even in the presence of moisture as
they are moisture-sensitive. To assure food safety, it is advised flavor molecules are significantly larger than oxygen molecules.
that these packages be tested under the worst condition of 100% EVOH is not considered a recyclable material; however, 0.001
RH for the full anticipated shelf life. inches of EVOH provides the same barrier protection as 4.5
Recently, the application of the nanocomposite concept was inches of HDPE (available from: www.foodproductdesign.com).
shown to be a promising option to improve mechanical and It is advocated to use either PE/paperboard/PE/tie layer/EVOH/tie
barrier properties of packaging films (Avella and others 2005). layer/PE/tie layer/EVOH in direct contact with the juice or a
Nanocomposite films were obtained by homogeneously dispers- slightly simpler structure consisting of PE/PP/tie layer/EVOH. The
ing functionalized layered silicates (clay minerals) in thermoplas- barrier is an excellent way to protect juice from losing flavor and
tic starch via polymer melt processing techniques. These films aroma compounds. Also, a relatively simple structure of HDPE/tie
were made by using different starch matrices such as potato starch layer/EVOH/tie layer/EVA protects against flavor migration.
and a mixture of potato starch with biodegradable polyester. In the McLean Marketing has announced a new concept in pack-
case of starch/clay nanocomposites, a good intercalation of the aging for Uncle Matt’s organic juices. The company is offering
polymeric phase into clay interlayer galleries, together with good its organic orange juice in PET bottles that are claimed to offer
mechanical parameters such as modulus and tensile strength, was many advantages, which for consumers could translate into bet-
obtained. Moreover, the conformity of the starch/clay nanocom- ter juice quality and taste plus an “easy to recycle” container.
posite films with actual regulations and European directives on The PET packaging produces better juice quality over the life of
biodegradable materials assessed demonstrated that these mate- the product, providing a better oxygen barrier with less flavor
rials could be utilized in the food packaging sector owing to their scalping.
low overall migration limit. Polymer nanocomposites have been demonstrated to help
Packaging for wines and liquors. Closure types vary consider- achieve packaged food a shelf life of 3 to 5 yr (Perchonok 2003).
ably in scalping properties and may cause considerable changes AegisTM OX polymerized nanocomposite, oxygen-scavenging
in flavor concentration in wines (Capone and others 2003). Clo- barrier nylon resin, specially formulated for high oxygen and car-
sures tested included screw caps, natural cork closures, a tech- bon dioxide barrier performance, even in high humidity, is com-
nical cork closure, and 7 synthetic closures. Semillon wine sam- mercially available for a host of co-injection molded PET bottle
ples spiked with various aroma compounds, including pyrazines, applications, including bottles and orange juice containers. An-
oak-related phenols, ethyl esters of fatty acids, monoterpenes, or other grade, AegisTM NC, can be used as a coating or as the base
hydrocarbons, and sealed with the closures under test were stored resin for cast or blown films and replace nylon 6 coatings in pa-
for 2 yr. No absorption of any of the flavor or aroma compounds perboard juice cartons. The new family of resins nearly doubles
on the screw caps was observed. Relatively nonpolar compounds the heat resistance of nylon 6 and has a potential for less flavor
were absorbed by cork or synthetic closures. The more polar com- scalping.
pounds were not absorbed by any of the closures. For the nonpo- For wines and liquor. A clear, high-barrier film that creates a
lar compounds, absorption was greatest for the synthetic closures; superior oxygen barrier to protect wine packaged in bag-in-box
technical cork closures performed similarly to the natural corks, wine casks is now available from Scholle Corporation (Chicago,
but had a slightly higher absorption capacity. Ill., U.S.A.), a supplier of wine bags worldwide (available from:
For pale ale bottled in clear PET and PEN containers with plastic www.bagnbox.com). This film replaces the traditional metallized
caps, and a glass control bottle with a crown closure, sensory, and PET film that used to be standard in the wine industry. It essen-
physicochemical properties at the 14th wk, showed PEN bottles tially doubles the shelf life of the wine, resists puncturing and
to have provided the best protection, followed by glass and finally flex-cracking, and can withstand the rigorous transportation con-
PET (Goodrich 1997). ditions required for export. DuraShield is now being used in wine-
Packaging for aseptic foods. Aseptic foods are packaged in a producing countries worldwide. Using the latest polymer tech-
variety of polymeric materials. The PE liner in brick type asep- nology, it reduces flavor scalping. However, Flextank, a world
tic containers scalps d-limonene, geranial, octanal, and decanal leader in using PE for wine aging, maintains that food-grade PE
from juice products (Arora and others 1991). As a result, the pack- of any density will retain its porosity in the presence of wine for
aged fruit juice lacks flavor notes characteristic of fresh juice. many years resisting clogging by wine components or scalping
There are reports of 62% and 37% sorption of nonpolar and po- flavor from the wine.
lar organics, respectively, by PP. PP is ranked second after PE in Cleartuf Power Polyester Resin (M&G Polymers USA, LLC,
the quantity of flavor compound sorbed. Juices packed in co- Tortona, Italy) is a PE terephthalate copolymer resin designed
extruded PP containers, consisting of PP outer and inner layers for liquor packaging and custom-packaging applications. It is a
surrounding an internal EVOH layer, have shown a marked de- high-molecular-weight polymer designed to provide highly desir-
crease in d-limonene content compared to juices packed in foil able container properties for the one-way packaging of tunnel-
containers due to sorption. A layer of Saran is suggested with PP pasteurized beers (available from: www.mgpolymers.com). These
and HDPE to reduce the sorption of d-limonene (Arora and others include high clarity and sparkle, increased temperature and pres-
1991). sure stability, reduced flavor scalping, reduced carbon dioxide
Commercial scalping-resistant packaging options. Some com- loss due to creep, and reduced carbon dioxide and oxygen perme-
mercial packaging materials are specifically designed to circum- ability. Cleartuf Power Polyester Resin is designed with a special
32 COMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY—Vol. 6, 2007
Scalping of flavors in packaged foods . . .

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