Oxygen and Carbon Dioxide Solubility and

Diffusivity in Solid Food Matrices: A Review

of Past and Current Knowledge
Estelle Chaix, Carole Guillaume, and Valérie Guillard

Abstract: Oxygen and carbon dioxide solubility and diffusivity are 2 key parameters to understand gas transfer in food
matrices. Knowledge of these parameters could help to predict gas concentration in modified atmosphere packaging and,
consequently, to predict shelf–life of the product through the development of appropriate mathematical models. The aim
of this review is to present the existing methodologies to quantify O2 and CO2 contents in food, especially in solid food
matrices which is very challenging. There is a focus on how these methodologies could be used to determine gas transfers
kinetics. Data of O2 /CO2 solubilities and diffusivities in food are collected and compared with a specific emphasis on
the food characteristics and factors impacting them. An analysis of the current state of knowledge in solid food matrices
is carried out to tentatively build a general predictive model of the O2 and CO2 solubility and diffusivity extendable to
any kind of food matrix.

Introduction gas exchange between headspace, external atmosphere, and food.

Modified atmosphere packaging (MAP) is used to protect per-
ishable food and extend its shelf–life (Badran and others 1969).
Air in the packaging is replaced by a specific gas or mixture of
gases (mainly CO2 , O2 , and/or N2 ) that should be close to the
optimal (or recommended) gas concentrations, specific to each
food and packaging (Soccol 2003). The objective of MAP is to
control the main reactions of food degradation, namely microbial
growth, oxidation, or also enzymatic reactions, and thus extending
the product shelf-life. However, maintaining the appropriate gas
composition in MAP is not easy since a gradient of gas concen-
tration is unavoidably created between the external and internal
atmospheres inducing some mass transfers through the packag-
ing material (that is, permeation). Even when using materials
with high barrier properties, which allows the maintenance of
the original internal atmosphere, gas transfers occur between the
headspace and the food product (that is, solubilization) and within
the food (that is, diffusion) leading to changes in headspace partial
pressures. The kinetic of this gas dissolution within the food
(which is desired for CO2 to gain the appropriate antimicrobial
activity) strongly depends on the value of diffusivity and the ge-
ometry of food. If permeation through packaging material could
not be neglected, this diffusivity, in addition with permeation
and solubility, is even more important to predict the dynamic of
MS 20131480 Submitted 10/17/2013, Accepted 12/20/2013. Authors are with
UMR 1208 IATE Agropolymers Engineering and Emerging Technologies, Univ.
Montpellier 2, CIRAD, INRA, Montpellier Supagro, CC 023 Place Eugène Batail-
lon, 34095 Montpellier Cedex 5, France. Direct inquiries to author Guillard (E-mail:
guillard@univ-montp2.fr).
Knowledge of overall mass transfers in food/MAP systems and
their mathematical modeling is necessary to predict gas concen-
trations in the headspace and gas gradients within food, and con-
sequently, to better comprehend shelf-life of the product (Sandhya
2010). Up to now, the right combination (initial gas content,
package surface/volume, mass of food, temperature) and espe-
cially the window of packaging permeabilities required that allows
to inhibit/delay microbial growth is principally determined with
the “pack and pray” empirical methodology which is time- and
cost-consuming (Ahvenainen 2003). Even if some modeling ap-
proach has been attempted to take into account the dissolution
of CO2 within food in predictive microbiology model (for exam-
ple, Devlieghere and others 1998), the dynamic of mass transfer
through the packaging and within food was never considered.
However, this is definitively indispensable when, for the same
food product, the packaging materials are changed. For example,
use of bio materials, and/or lightened material leads to signif-
icant change of materials properties and thus permeabilities. In
the field of respiring foods (for example, fruits and vegetables),
mass balance models have been developed—by coupling math-
ematical models for gas permeation through the packaging ma-
terial (based on Fick’s law) and for gas consumption/production
by the food (based on the Michaelis–Menten-type equation)—
and are already available online such as www.packinmap.com
(Mahajan and others 2007) or www.tailorpack.com (Cagnon
2012). They can be used to predict either change in gas composi-
tion of the packaged respiring food or gas permeability values that
will allow the establishment of the optimal gas concentration. In
the field of MAP for nonrespiring food (for example, meat-based
food), such mass balance models, that would take into account


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doi: 10.1111/1541-4337.12058 Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 261
O2 and CO2 solubility and diffusivity . . .
both permeation, solubilization, and diffusion, have not yet been
well developed and implemented, despite the increasing interest
in the development of decision aid tools. This is mainly due to
the lack of data on solubilization and diffusion for different food
products.
Three phenomena govern the gas transfers in the nonrespir-
ing food/MAP system: gas permeation—through the pack-
age between the exterior atmosphere and the headspace, gas
solubilization—between the headspace and the food product, and
gas diffusion—within the food product; each of them character-
ized by physical constants: permeability, solubility, and diffusivity
coefficients, respectively. If the knowledge of permeability coeffi-
cient in classic polymers is well referenced (Massey 2003), data of
O2 and CO2 solubility and diffusivity coefficients in food prod-
ucts are lacking, except in the case of water. As shown in Figure 1,
there are 70 values for O2 solubility in food/model products (49
in liquid, essentially fish and vegetable oils, and 21 in solid matri-
ces) in the available scientific literature (which corresponds to 10
cited papers on the topic), whereas, as shown in Figure 2 a and b,
more than 115 values are available for CO2 solubility (that is, 11
cited papers) just in solid food matrices (69 in high–water-content
foods and 50 in high–fat foods). Data on CO2 are more common
than for O2 , this might be attributed (i) to the great interest for
CO2 in MAP because of safety concerns (bacteriostatic activity),
whereas O2 in MAP is mainly related to organoleptic changes
(but also to inhibit fat oxidations) (Ahvenainen 2003), and (ii)
the difficulty to control O2 partial pressures (residual O2 , possible
oxidation, and so on). With regard to diffusivity, very few values
are available for both the gases (26 values for O2 diffusivity in
food/model matrices, 10 in liquid food and 16 in solid matrices;
and 30 for CO2 , essentially in real solid food matrices (25 values)
(Figure 3 and 4). Contrary to solubility, the diffusivity cannot be
directly measured from experiments. It is identified from numer-
ical treatments of transient kinetic data acquired when the sample
is subjected to a gradient of gas concentration (or partial pressure).
Whatever the solubility measurement or diffusivity identification,
methodologies for O2 /CO2 assessment and specific set–up for
controlling the gas environment are needed but scarcely reviewed,
especially for solid food. We noted a publication on measurement
of CO2 in liquid or gaseous media (Dixon and Kell 1989a), a
list of diffusion and solubility values for various gases, including
CO2 and O2 , in biological fluids and tissues (Langø and others
1996), a review on CO2 sensors used in the agri–food industry
(Neethirajan and others 2008), a research note on CO2 trans-
fer in MAP systems and nonrespiring food (Simpson and others
2009), and a review, published in 2012, which described O2 quan-
tification methods and their applications to obtain the O2 diffu-
sivity and solubility coefficient in liquid food product (Pénicaud
and others 2012).
In this context, this work proposes an overall presentation of
methods and/or guidelines devoted to measurements of O2 and/or
CO2 content in food and/or determination of O2 and/or CO2
solubility and diffusivity in food, and principally in solid food
matrices. An emphasis will be put on how these methodolo-
gies could be implemented in experimental setups to monitor
O2 and CO2 transfers, and then determine diffusivity coeffi-
cients, which had never been done before for both gases si-
multaneously in a same report. After a brief introduction of
the basics on gas solubilization and diffusion, this review will
focus on gas quantification and solubility/diffusivity determina-
262 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014
tions of O2 and CO2 with an emphasis on factors affecting these
coefficients and associated mathematical models for prediction
purposes.
Basics of Mass Transfer
O2 and CO2 diffuse from the surrounding atmosphere to liq-
uid and solid foods, where they dissolve. The driving force of
this phenomenon is the difference in the chemical potential (or
activity) between the surrounding atmosphere and the medium.
O2 and CO2 dissolve in the medium until equilibrium be-
tween partial pressure in headspace and dissolved concentration
in food is reached. Henry’s law was first demonstrated to de-
scribe this relationship in a dilute solution (Henry 1803) and is
today extended to any kind of product: at equilibrium and for
constant temperature and pressure (Eq. 1) the concentration of
dissolved gas A in a solvent (CA ) is proportional to its partial
pressure (PA ) in the solvent (and consequently in the surrounding
atmosphere)
1
P A = kHA (T) × C A = × CA (1)
SA
where kHA (T) is Henry’s law coefficient of the gas A in a solvent
at temperature T. Solubility coefficient (SA ) is the inverse func-
tion of Henry’s law coefficient, kHA (T) = 1/SA , and expressed in
mol.kgfood –1 .Pa–1 (international unit system, but other units can be
found). It represents the maximal quantity of gas A that could be
dissolved in a solvent, for a given partial pressure of A, and reflects
the compatibility between the gas molecule and the food matrix
(Schwartz 2003; Rotabakk and others 2006; Pénicaud and oth-
ers 2012). While Henry’s law is widely admitted, its validation is
still mandatory. Up to now, it has been validated for CO2 in water
(Carroll and others 1991) and various food products such as cheese
and fresh pasta (Fava and Piergiovanni 1992), fish (Sivertsvik and
others 2004b), raw meat (Fava and Piergiovanni 1992; Zhao and
others 1994), and cooked meat (Sivertsvik and Jensen 2005). In
the case of O2 , Henry’s law was validated in water and aqueous
solution (microbial culture media) (Schumpe and others 1982),
in various organic liquids (such as acetone or ethanol) (Lühring
and Schumpe 1989), and in soybean oil (Ke and Ackman 1973).
Some studies reported a slight deviation from Henry’s law, and
identified a linear correlation, with a deviation from the ori-
gin, between partial pressure and CO2 concentration in certain
cheeses (Jakobsen and Jensen 2009), or O2 concentration in veg-
etable purees (Samapundo and others 2011). Values of solubility
coefficient encountered in the literature for different food/model
matrices are indicated in Figure 1 (for O2 ) and 2a and 2b (for
CO2 ).
Gas diffusivity coefficient is a nonthermodynamic kinetic pa-
rameter which indicates gas mobility in food matrices. This trans-
fer is due to the influence of a gradient of concentration of the
considered gas. It is usually described by the well–known Fick’s
second law (Fick 1855), which connects local changes of cA , vol-
ume concentration of the gas A (kg.m–3 ), as function of time
(s), and x, the distance between the interface and measurement
point (m) with D, the diffusion coefficient (m2 .s–1 ), according
to Eq. 2:
∂cA ∂ 2c A
=D 2 (2)
∂t ∂x

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O2 and CO2 solubility and diffusivity . . .

Figure 1–Oxygen solubility, as a function of temperature, standard deviation, when available, and in brackets methodology used, in various food
matrices. [a] (Battino and Clever 1966); [b] (Ke and Ackman 1973); [c] (Davidson and others 1952); [d] (Battino and others 1968); [e] (Aho and
Wahlroos 1967); [f] (Simpson and others 2001a); [g] (Zaritzky and Bevilacqua 1988); [h] (Fabiano and others 2000); [i] (Samapundo and others
2011); [j] (Sidwell and others 1962). p.v. stands for peroxide values and RH stands for relative humidity.

Considering this kinetic description and unlike to the solubility,
the diffusivity cannot be directly measured. For this, a gradient of
concentration or partial pressure must be imposed to the sample,
and the subsequent mass transfer must be measured against time
and/or position. The diffusivity is then identified by comparing
the theoretical data (predicted by a mathematical model, usually
the Fickean model) and the experimental data (see section “Exper-
imental set–up of O2 /CO2 diffusivity”). The diffusion coefficient
is, for example, the one that minimizes the sum of squared er-
ror between the 2 datasets. In combination with difficulties to
set up the experiment, the time–consuming data acquisition and
treatment may explain why there are so few diffusivity values avail-
able in the literature either for O2 (mainly on fruit and vegetable
products, Figure 3) or CO2 (presented in Figure 4). The following
presents an overview of the main methodologies used for O2 /CO2
quantification with an attempt, as far as possible, to describe the


C 2014 Institute of Food Technologists® Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 263
O2 and CO2 solubility and diffusivity . . .

Figure 2–(a) Carbon dioxide solubility, as a function of temperature, standard deviation, when available, and into brackets methodology used, in
various high–water–content food matrices. [a] (Carroll and others 1991); [b] (Geankoplis 1993); [c] (Pauchard and others 1980); [d] (Simpson and
others 2001a); [e] (Fava and Piergiovanni 1992); [f] (Gill 1988); [g] (Sivertsvik and Jensen 2005); [h] (Simpson and others 2009); [i] (Piergiovanni
and Fava 1992); [j] (Rotabakk and others 2010); [k] (Sivertsvik and others 2004b); [l] (Simpson and others 2001b).

pros and cons of each methodology with a special emphasis on
the facility of handling and implementation of each set-up, pos-
sibility to carry out direct measurement and feasibility to be used
in solid food product (which is actually the tricky point). All this
information is summarized for CO2 in Table 1 and 2. The same
analysis was already done for O2 by Penicaud and others (2012)
and was, thus, not repeated in the present work since no update
was necessary to their work at the time being.
Oxygen and Carbon Dioxide Quantification Methods in
Food Matrices
O2 quantification methodologies together with solubil-
ity/diffusivity determination in liquid food/model matrices have
been recently reported by Pénicaud and others (2012). Several
methods could be used for determining CO2 concentration in
a liquid or gas phase, and they are almost all well described in
the review of Dixon and Kell (1989a) while Neethirajan and

264 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014 
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O2 and CO2 solubility and diffusivity . . .

Figure 2–(b) Carbon dioxide solubility, as a function of temperature, standard deviation, when available, and into brackets methodology used, in
various high–fat–content food matrices. [a] (Fabiano and others 2000); [b] (Battino and others 1968); [c] (Pauchard and others 1980); [d] (Jakobsen
and Jensen 2009); [e] (Fava and Piergiovanni 1992); [f] (Gill 1988); [g] (Piergiovanni and Fava 1992).

others (2008) listed various types of CO2 sensors used in the
agri–food industry. They pointed out that while several O2 /CO2
quantification methods exist, few directly detect and quantify the
O2 /CO2 molecule (either partial pressure or concentration). Bias
and interferences have to be considered in most of the techniques.
The following section will address a brief recall and update of
their work (section “Direct measurements of O2 /CO2 ”). The im-
plementation of these methodologies in dedicated experimental
setups for assessing both O2 /CO2 solubility and diffusivity coeffi-
cients in solid food will be presented and discussed. This remains
the tricky point for mass balance model developments, and will be
further discussed in sections “Experimental Set–Up for O2 /CO2
Solubility Determination in Solid Foods” and “Experimental set–
up of O2 /CO2 diffusivity,” respectively.
Quantification methods of O2 /CO2 can be divided into 2
main categories: (a) direct measurements that refer to method-
ologies that permit to access the molecular O2 /CO2 concen-
tration within a given mass of food/model and (b) indirect


C 2014 Institute of Food Technologists® Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 265
O2 and CO2 solubility and diffusivity . . .

Figure 3–O2 diffusivity values in nonrespiring food or simulants (liquid or solid), as a function of temperature, and some examples of value in fruit.
Adapted and compiled from Pénicaud and others (2010). [a] (Langø and others 1996); [b] (Baird and Davidson 1962); [c] (Barront and others 1993);
[d] (Brown 1955); [e] (Crowe and others 1987); [f] (Davidson and Cullen 1957); [g] (Davidson and others 1952); [h] (Geankoplis 1993); [i] (Grote and
Thews 1962); [j] (Grote 1967); [k] (Lightfoot 1974); [l] (Mannapperuma and others 1991); [m] (Miller and others 2003); [n] (Pénicaud and others
2010); [o] (Sato and Toda 1983); [p] (Schotsmans and others 2004); [q] (Valleguadarrama and others 2005); [r] (Wise and Houghton 1969); [s]
(Zaritzky and Bevilacqua 1988); [t] (Adlercreutz 1986).

measurements that refer to methodologies that permit to ac- measurement of CA in Henry’s law). Few direct methodologies
cess the O2 /CO2 partial pressure or concentration within the are available for quantification of molar quantity of both gases
headspace (or few times the O2 /CO2 partial pressure within the within a matrix: titration or absorbance spectrophotometry after
food/model). chemical reaction, gravimetry, and for CO2 only infra–red mea-
surements.
Direct measurements of O2 /CO2 Chemical reactions. Direct measurements for O2 are known
We call “direct measurement” a method that permits the as colorimetric methods, Winkler test, or gravimetry; neverthe-
molecular quantification of O2 or CO2 in the medium (direct less, the chemical one, the Winkler test, remains the reference to

266 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014 
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O2 and CO2 solubility and diffusivity . . .

Figure 4–CO2 diffusivity values in nonrespiring food or simulants (liquid or solid), as a function of temperature, and some examples of values in fruit.
[a] (Bertola and others 1990); [b] (Brown 1955); [c] (Carroll and others 1991); [d] (Fabbri and others 2011); [e] (Fabiano and others 2000); [f]
(Geankoplis 1993); [g] (Mannapperuma and others 1991); [h] (Schotsmans and others 2004); [i] (Simpson and others 2001b); [j] (Simpson and others
2001a); [k] (Sirivicha and others 1990); [l] (Sivertsvik and others 2004b); [m] (Sivertsvik and Jensen 2005); [n] (Solomos 1987); [o] (Treybal 1980).

quantify O2 dissolved in water. It exploits the ability of manganese
(II) salt to react (a) in a basic medium (presence of hydroxide solu-
tion, for example, sodium hydroxide or potassium hydroxide) with
dissolved O2 contained in the sample and (b) to form a brown pre-
cipitate. This further reacts with iodide ions, previously added, in
the presence of acid to produce iodine, which is then quanti-
fied by a titrated thiosulfate solution (Battino and Clever 1966).
This extraction and titration is difficult because it must be done
without O2 exchange between the sample and the surrounding
atmosphere.
In the second example of direct chemical measures, the CO2 is
trapped in and reacts with a scavenger, mainly liquid–based: bar-
ium dihydroxide (Ba(OH)2 ), KOH, NaOH, or calcium hydroxide
(Ca(OH)2 ), which is then assayed most of the time by chemical
titration. One main drawback remains nevertheless unavoidable:
overestimation of the quantity of CO2 really dissolved in the sam-
ple due to the leaching of existing carbonate ion (CO3 2– ), bicar-
bonate ion (HCO3– ), or carbonic acid (H2 CO3 ) in the sample due
to their unavoidable conversion into CO2 during the acidification
step. To correct the measured CO2 content by the amount of
initial CO3 2– , HCO3– , or H2 CO3 initially present in the sample,
it is necessary to titrate a sample which has not been in contact
with CO2 before (except the unavoidable contact with a small
amount of atmospheric CO2 ). In the case of use of Ba(OH)2


C 2014 Institute of Food Technologists® Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 267
O2 and CO2 solubility and diffusivity . . .

Table 1–Different methods used in the literature to obtain CO2 concentration, with emphasis on measurement phase.

Measurement mediuma
Methods Precision Principle Reference for description Gas Liquid Solid
Direct Infra-red FTIR- ATR Sample absorption of (Brantley and others 2000) x x x
spectrometry IR radiation in situ
Raman Sample absorption of (Beutel and Henkel 2011) x x X
radiation and shift
of energy in
function of
vibrational modes
NDIR Desorption of sample, (Watten and others 2004) x
absorption of IR
radiation by CO2
headspace
Gravimetric Weight change by (Dixon and Kell 1989) x x
absorption/release
of CO2
Indirect Gravimetric Piezoelectric Weight change in (Fanget and others 2011) x x x
resonant frequency
due to adsorption of
CO2
Chromatography Katharometer (TCD) Differences in thermal (Girard and Boyaval 1994) x
conductivity
Mass spectroscopy Characterization by (Dixon and Kell 1989) x
the mass to charge
ratios and relative
abundances
Manometric Increase/Decrease (Sivertsvik and others 2004a) x
headspace pressure
above an acidified
sample
Volumetric Increase/Decrease in (Dixon and Kell 1989) x
volume of a gas
sample after
chemical removal of
CO2
Chemical titration A standard alkaline (Gill 1988) x
solution is
neutralized after
absorbing CO2
Amperometric (Clark Type) Electron transfer due (Ishiji and others 1993) x
to reduction of CO2
in aqueous solution
and measure of
electric flow
Potentiometric (Severinghaus type) pH changes in buffer (Puligundla and others 2011) x
solution induced by
CO2
Colorimetric Color change of pH (Dixon and Kell 1989) x x
indicator (solution
or materials)
Fiber optic probes Changes in light (Neethirajan and others 2008) x
transmittance of pH
indicator
Enzymatic Spectrophotometric Absorbance change (Forrester and others 1976) x
by consumption of
NADH to NAD+ by
the enzyme
(function of CO2 )
a Refers to the phase where the CO is quantified.
2

solution, the “aging” between the beginning and the end of the
experiment induces a change in its molality. To assess the aging of
the Ba(OH)2 solution, it is thus necessary to titrate the Ba(OH)2
solution before and after the experiment.
Gravimetry. Another methodology used for direct quantifica-
tion of O2 or CO2 inside solid food products (but that could be
also used in certain cases for a liquid) is gravimetry. The princi-
ple of this method is to sorb O2 or CO2 in a matrix of known
and precise mass. At equilibrium, the sample mass increases due
to the incorporation of gas and may thus be used to calculate
the O2 or CO2 solubility. The matrices must be devoid of O2 or
CO2 . That could be achieved during the desorption step under a
flux of gas free of O2 or CO2 (dynamic mode) or under vacuum
(static mode). The gravimetric method is a simple, direct, and
powerful experimental procedure. It permits to measure the O2
or CO2 solubility, but also the O2 or CO2 diffusivity when the
mass uptake is monitored. One of the main requirements neces-
sary for this methodology is the accuracy of the balance. Currently,
some commercial equipment (that is, Cahn microbalance, Hiden
Isochema gravimetric microbalance, and so on) enables to perform
such an experiment with a sensitivity less than 0.1 μg (Shiflett and
Yokozeki 2005).
Infra–red measurement. Infra-red measurement does not ap-
ply for the quantification of the O2 molecule. The principle
of infra–red measurement is based on the energy absorption of
the CO2 molecule and its asymmetrical stretching, at a known
wavelength (2.4 μm) (Neethirajan and others 2008). For mea-
surement of gaseous CO2 , infra–red spectroscopy–based captors

268 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014 
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O2 and CO2 solubility and diffusivity . . .
are the most commonly used. An alternative method is gas chro-
matography, generally coupled with a thermal conductivity de-
tector or mass spectrometry (section “Chromatography measure-
ment”). Both methodologies can permit the quantitative and
qualitative analysis of gaseous CO2 (% CO2 ). To obtain CO2
quantification via the intensity of the stretching band, the infra–
red sensor prerequires calibration which is a time–consuming pro-
cess (Yasuda and others 2012) but usually is made by suppliers.
Infra-red sensors are conventionally used for gaseous detection
and control in the laboratory and industry because most com-
mercial CO2 analyzers are based on this technology; for example,
we can obtain headspace analyzers such as “oxygen and carbon
dioxide headspace gas analyzer” from Illinois Instruments (Johns-
burg, Illinois, U.S.A.), “CO2 Gas sensor” from Vernier (Beaver-
ton, Oregon, U.S.A.), “CheckMate” from PBI Dansensor (Ring-
sted, Denmark), or “Pac Check” series from Mocon (Minneapolis,
Minnesota, U.S.A.). (PBI Dansensor (Ringsted, Denmark) has re-
cently been bought by Mocon (Minneapolis, Minnesota, U.S.A.).
Calibration time is reduced by self–calibration of commercial de-
vices, which display good sensitivity and accuracy (from ± 2% to
0.8% for the most precise). Nevertheless, they require a large gas
sample volume (around 5 to 10 mL) for analysis and interferences
could appear with water vapor (dilution effect) (Mills and Hodgen
2005). When used for headspace analysis in a sealed package, the
measure can be destructive, by the direct insertion of a syringe, or
not, by using a septum. However, in any case, the method is con-
sidered as destructive because of the too large sampling leading to
considerable change in the headspace volume. Infra–red headspace
analyzers remain the cheapest gas analyzers compared to other sys-
tems such as gas chromatography, gravimetry techniques, and so
on.
Fourier transform infra–red–attenuated total reflection (FTIR–
ATR) spectroscopy is a powerful tool for studying molecules ab-
sorbed into solid matrices. The spectrum of dissolved CO2 is well
characterized in mid–infrared and can be identified by the ab-
sorbance in the spectral region 2300 to 2350 cm–1 . It is widely
used in the field of polymer and membrane science to measure
CO2 transfer within thin films or plane sheets (Pasquali and others
2008; Karimi 2011). The solid sample is in contact with the ATR
crystal and must be homogeneous and flat, so that the “thick film
approximation” theory can be applied (Ferrari 2009). This type
of spectrometer offers precise detection of CO2 at ppb levels, and
the possibility to measure multiple molecules simultaneously (Mc-
Donagh and others 2008). Furthermore, the monitoring of CO2
sorption kinetics as a function of time in the sample can be easily
performed and thus determination of diffusivity could be achieved
(Karimi 2011). However, as for all spectroscopic methodologies,
FTIR–ATR should be first calibrated using another technique in
order to gain some quantitative values of dissolved CO2 . Another
problem occurs in view of CO2 dissociation in aqueous media into
different carbonate species, and the molecules associated with CO2
becoming visible at different wavelengths (Wijnja and Schulthess
1999).
Indirect measurements
For the measurement of gaseous CO2 , infra–red spectroscopy–
based captors are the most commonly used. Alternative methods
for both O2 /CO2 content are (a) gas chromatography that needs
an extraction of the sample and a gaseous calibration to quantify,
(b) manometric and volumetric methods. Both methodologies can
allow the quantitative and qualitative analysis of gaseous O2 /CO2
(% O2 /% CO2 ).

C 2014 Institute of Food Technologists® Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 269
Chromatography measurement. As for O2 , gas chromatogra-
phy is the most widely used technique in the laboratory to mea-
sure CO2 content in a gaseous phase. The main interest of this
technique is the possibility to simultaneously measure different
gases (for instance, O2 and CO2 ). After separation, molecules are
detected, generally by katharometer (measure of thermic conduc-
tivity), but also by flame ionization (FID) or by mass spectrometer,
the most frequently used. If the gas chromatography apparatus has
a low cost, detectors are more expensive. Furthermore, the analysis
of O2 /CO2 content in samples (liquid or solid) by gas chromatog-
raphy is time–consuming because it requires an extraction step
(Ruyssen and others 2013) and periodic calibration (Neethirajan
and others 2008). As with quantification by infra–red measure-
ment, gas chromatography applied to the system food/package is
also an intrusive and destructive measurement, even if volumes of
samples are low (about 10 μL).
Manometric and volumetric methods. Manometric and volu-
metric approaches are the oldest methodologies developed to in-
vestigate sorption of gases in solids. The quantification of O2 /CO2
absorbed or desorbed by a sample is obtained from the difference
in total pressure (manometric method) or volume (volumetric
method)—at a constant volume (manometric method) or pres-
sure (volumetric method)—in the gas phase, in contact with the
sample, between the beginning and the equilibrium. This implies
the following main assumptions: the gas follows (a) ideal gas law
and (b) a compressibility factor equal to 1 (Sivertsvik and oth-
ers 2004a). Moreover, one difficulty is to keep constant the exact
known volume of the closed container used in the manometric
method or the pressure in case of the volumetric method. Both
volumetric and manometric methods are approved by the AACC
Intl. Organization for Standardization Measurement (respectively,
AACC Method 22–11.01 and 22–14.01) with the advantages that
they (a) are easy to implement and (b) do not require sophisti-
cated high–tech equipment, especially for the volumetric method
(Keller and Staudt 2005). However, possible bias can occur in both
cases from (a) an inaccurate evaluation of the container volume
or pressure (b) an unwanted release of volatile molecule from the
sample, and (c) uncontrolled leaks of the container (Dixon and Kell
1989b). Moreover, we noted that it is necessary to have a signif-
icant pressure or volume modification to perform some accurate
solubility calculation. Thus the volume of the container used for
this experiment, as well as the mass of the sample, must be adapted
according to the expected amount of dissolved O2 /CO2 in the
assay.
pH–based sensor. Among the main indirect measurements for
CO2 , pH–based electrodes are one of the most current. The first
CO2 sensor based on potentiometric measurement was developed
by Severinghaus and Bradley in 1958. This electrode was initially
used to measure dissolved CO2 in blood. The measuring principle
is based on pH–value modification of a buffer solution trapped in
the probe, following CO2 dissolution. Dissolved CO2 is hydrated
into carbonic acid, bicarbonate ion, and carbonate ion, with lib-
eration of protons, which are detected by the probe (Eq. 3).
CO2 + H2 O ↔ H2 CO3 ↔ H + + HCO3− ↔ 2H + + CO32−
(3)
Severinghaus–type probes were then miniaturized: from 1 to
1.5 mm of diameter in 1974 (Caflisch and Carter 1974) to be-
tween 50 and 300 μm of diameter (Irimia-Vladu 2006). Their
main advantages are simplicity of handling and good detection
limit (around 10 μmol) (Janata 2009). Drawbacks are, first, a
slow response time (time-lag due to CO2 diffusion in the probe),
 Table 2–Main advantages and drawbacks of methodologies commonly used to quantify CO2, with emphasis on the facility of their use for solid food products (“D” stands Direct and “I” stand Indirect).

Methods Precision Cost Advantages Drawbacks Example of matrix studied

Food (if available), italic (if nonfood)

D Infra-red spectrometry FTIR- ATR ++ – Possibility of monitoring the kinetic of – Necessity to have an intimate contact Olive oil (Hennessy and others
adsorption between sample and crystal (for FTIR- 2009)
– Possibility to measure multiple molecules ATR technique)
Raman simultaneously – Calibration required Sea water (Dunk and others 2005)
O2 and CO2 solubility and diffusivity . . .

+++
– Difficulty to analyze the spectral signature
of CO2 and its dissociated species (visible
at different wavelengths)
NDIR + – The cheapest gas analyzers – Large gas sample volume required Cheese (Vivier and others 1996)
– Easy to handle (for commercial apparatus) – Possible interferences with water vapor Fresh scallops (Simpson and others 2007)
– Fast methodology – Difficult implementation for measuring Water, Cheese, Whey, (Pauchard and others 1980)
CO2 in solid food Butterfat, Olive oil
D Gravimetric +++ – Simple, easy to adapt for solid – Cost Olive oil (Yokozeki and Shiflett 2011)
food – Lack of molecular specificity
I Gravimetric Piezoelectric +++ – Possibility of monitoring the kinetic of Polymers (Aubert 1998)
adsorption

270 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014
I Chromatography Katharometer (TCD) ++ – Common technique in laboratory for gas – Time-consuming (due to the desorption step Cheese (Girard and Boyaval 1994)
phase analysis that could be long) Tomato (Bertola and others 1990)
– Accurate – Difficult implementation for measuring CO2 Potatoes (Sirivicha and others 1990)
– Low gas volume required for measurement in solid food.
Mass Spectroscopy +++ Cheese (Tammam and others 2001)
I Manometric + to ++ – Reference method (AACC Method 22 14.01) –Difficulty to keep constant the exact known Cooked meat product (Sivertsvik and others 2004b)
– Easy to implement volume of the closed container,
– Possible bias can occur due to lack of
inaccuracy in container volume evaluation,
– Unwanted release of volatile molecule and Raw meats, Cheeses, (Fava and Piergiovanni 1992)
uncontrolled leaks of the container Pastas, Cooked cold


– Necessity to have a significant pressure meats
modification to perform some accurate
solubility calculation Pesto sauce (Fabiano and others 2000)

C 2014 Institute of Food Technologists®

 
Table 2–Continued

Methods Precision Cost Advantages Drawbacks Example of matrix studied

Food (if available), italic (if nonfood)
I Volumetric + to ++ – Reference method (AACC Method 22 11.01) – Possible bias can occur due to lack of Cod (Rotabakk and others 2007)
– Easy to implement inaccuracy in container pressure
– Could not require sophisticated high tech measurement

C 2014 Institute of Food Technologists®

equipment – Unwanted release of volatile molecule and
uncontrolled leaks of the container
– Necessity to have significant volume
modification to perform some accurate
O2 and CO2 solubility and diffusivity . . .

solubility calculation
Chicken fillets (Rotabakk and others 2010)
I Chemical titration – – Reference method –Possible overestimation of the quantity of CO2 Meat/Cheese/Egg (Gill 1988)
– Easy to handle due to leaching of carbonates from the food
– The less expensive methodology product: necessity to realize a blank sample
– Easy to adapt for measuring CO2 in solid food – Labor cost
– Time-consuming
Cheese (Jakobsen and Bertelsen 2004)
Egg (Keener and others 2001)
I Amperometric (Clark Type) – /+ – One of the more current indirect measurement – Slow response time (time-lag due to CO2 Blood plasma (Fasching and others 2003)
for CO2 in liquid phase diffusion in the probe)
– Miniaturized system possible – Invasive method (problem for bulky probe)
(micro-electrodes) – CO2 is not directly detected but its ionic forms
indirectly
I Potentiometric (Severinghaus type) – /+ – Simplicity of handling, good detection limit – Lack of stability and shorter life for Fish fillet (Wang and Ogrydziak 1986)
(around 10 μmol) micro-electrodes compare to
macro-electrodes
– disruptions due to other dissolved species that
induce pH change
I Colorimetric – to + – Cheap method – Not suitable for continuous measurement Soils (Rowell 1995)
– Could not require sophisticated high tech – Time consuming
equipment – Calibration curve
I Fiber optic probes – /+ – Nondestructive, noninvasive – Relies on pH change: CO2 is not directly Pears (Ho and others 2007)
– Better sensitivity to dissolved CO2 than detected and disruptions due to other
ph-based electrode (Severinghaus type) dissolved species that induce pH change
could occur
I Enzymatic Spectro-photometric – to + – Easy to handle (for commercial apparatus) – Could be time-consuming (biological Cheese (Crow and Martley 1991)
– Could not require sophisticated high tech molecule)
equipment – Unsuitable for continuous use
– Specific for CO2 – Calibration curve

Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 271
O2 and CO2 solubility and diffusivity . . .
second, the fact that it is an invasive method (bulky probe), and,
then, CO2 is not directly detected but its ionic forms indirectly.
Some micro–electrodes have been developed to overcome the
main drawback of their size, but they are unstable and have a
shorter life compared to macro–electrodes (Zhao and Cai 1997).
Commercial Severinghaus–type electrodes exist, for example, “V–
SignTM Sensor” by Artemis (Kent, United Kingdom) for partial
pressure CO2 measurement in medical application or “Sonde CO2
InPro 5000” by Mettler Toledo (Paris, France) design for biotech-
nological and fermentation controls.
Generally, the measure of CO2 content with a pH–measurement
system is affected by other dissolved species that induce pH
changes, for example, volatile acid or basic gases, modification
of acid present in the medium with addition of CO2 , or im-
pact of salt conditions (osmotic pressure), but also by biologi-
cal processes that may lead to changes in CO2 content and/or
pH (acid production by microorganisms, proteolysis, and others)
(Mills and Hodgen 2005; Neethirajan and others 2008; Oludare
and others 2009). To avoid pH interference, recent developments
on optical–based CO2 –sensors tend to directly quantify CO2 or
its ionic forms in a medium instead of protons (section “Optical
sensors”).
Optical sensors. Recent O2 /CO2 sensors based on optical mea-
surements allow nondestructive measurements and, in some cases,
also noninvasive ones. A variety of optical sensors exist to detect
CO2 or ionic forms, exploiting different detection methodologies,
such as colorimetric, infra–red, fluorescence, or pH–based ones
(Burke and others 2006). For example, in this last case, a sens-
ing element (pH–sensitive fluorescent indicator or organometal-
lic complexes) reacts with gaseous CO2 and/or its ionic forms,
which induces a modification of its absorbance or reflectance. This
change is quantified by an amber light–emitting diode, which re-
lates modification of the emitted signal to the CO2 concentration
(Neethirajan and others 2008). Optical O2 /CO2 sensors are still
essentially lab–made, but some commercial products are appear-
ing such as for CO2 “FCO2 –R,” a nondestructive probe (Ocean
Optics, Duiven, The Netherlands) and “CO2 sensors,” nonde-
structive and noninvasive (PreSens, Regensburg, Germany), or
for O2 “Optical Oxygen Analyzer,” noninvasive (Oxysense, Dal-
las, Texas, U.S.A.) and “Non-Invasive Oxygen Sensors” (PreSens,
Regensburg, Germany). This latter (a small dot of 5 mm diam-
eter) is based on luminescence quenching and up to now ap-
pears to be the most promising method to obtain a measure of
CO2 partial pressure in situ for liquid and viscous food matri-
ces. This luminescence methodology relies on the permeation of
CO2 molecules through a membrane protecting a gel with a lu-
minescence complex. It particularly relies on the gel–induced pH
variation combined with Förster resonance energy transfer. More
precisely, CO2 molecules are trapped into the gel phase contain-
ing 2 dyes (ruthenium(II) polypyridyl complexes and a colorimet-
ric indicator, m–cresolpurple) and decrease the pH value of this
medium. This variation induces a change in the proton transfer,
between the ruthenium (II) polypyridil complex (proton donor)
to the gel–immobilized colorimetric indicator (proton acceptor).
This transfer induces a spectral shift of the colorimetric indicator
with a concomitant change of the proton donor, and also a vari-
ation of Förster resonance energy transfers. This variation can be
correlated to the amount of CO2 in the gel medium (Liebsch and
others 2000). It should be pointed out that the membrane is not
permeable to CO2 ionic forms (for example, HCO3 – ) but only to
CO2 gaseous molecules. Consequently, to obtain CO2 solubility,
this sensor can only be used for acid products (pH–value lower
272 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014
than 5) in which the main form of carbon dioxide is gaseous CO2
(Figure 5). This system was compared with the Severinghaus–type
sensor, and it displayed better sensitivity to dissolved CO2 in water
(Long and others 2012). A major constraint of these O2 /CO2 sen-
sors is that the spot should be placed inside a transparent container.
Measurement in the gas phase is possible, but the sensor needs a
sufficient relative humidity for the possible pH variation detection
by the sensor spot. We may suppose that O2 /CO2 partial pres-
sure measurement in high moisture solid matrices could also be
possible.
Experimental Set–Up for O2 /CO2 Solubility Determi-
nation in Solid Foods
Determination of O2 /CO2 solubility requires implementation
of an experimental set–up to (a) bring the sample into equilib-
rium with an atmosphere of controlled O2 /CO2 partial pressure
and (b) assay the concentration of dissolved gas into the sample.
Henry’s law is accepted for both gas solubility determinations;
the experimental set–up must allow obtaining headspace partial
pressure and concentration of dissolved gas into the solid food. It
is worth noting that implementation for O2 solubility assessment
is more difficult than for CO2 , because of the risk of “O2 sam-
ple contamination” by air during the assay: 20.358 ± 1.197% for
O2 and 0.793 ± 0.680% for CO2 in Europe (Fonseca and others
2000). The difficulty of measuring dissolved O2 and monitor-
ing O2 transfer in food without contamination from atmospheric
O2 has prevented the implementation of routine/standard meth-
ods. The following section will focus on the use of the above–
mentioned methodologies (section “Oxygen and Carbon Diox-
ide Quantification Methods in Food Matrices”) in experimental
set–up for gas quantification, and mainly the interest of the indi-
rect ones to access O2 /CO2 solubility in solid food, and also the
presentation of destructive and nondestructive food set–up.
Equilibrium set–up
As mentioned in section “Basics of Mass Transfer,” to obtain
the solubility value, the headspace/food system must be at equi-
librium. That implies there is no gaseous exchange between the
headspace (partial pressure is constant) and the matrices (intrinsic
concentration is also constant). The experimental set–up must al-
low reaching a steady state, while permitting the quantification of
both partial pressure and concentration of gases at the equilibrium
(the end of the experiment). From a general point of view, we
could divide the experimental set–up into 2 categories: (a) static
methods, in which gaseous mass balance of headspace/food sys-
tem is maintained constant over time and (b) dynamic methods,
where a gas flow rate is imposed in the headspace, and so the
mass–balance increases with time.
On the one hand, static (or batch) methods are easier to imple-
ment: for example, a food sample which was sealed in a container,
with gaseous concentration, volume and/or pressure of headspace
could be measured without opening it. To obtain equilibrium, gas
transfer occurs between the headspace and food, until the latter is
saturated: concentrations in food increase while gas partial pressure
of headspace decreases with time. In such conditions, final partial
pressure is not user–defined and depends on the gas solubility in
food.
On the other hand, dynamic experiments enable to force the
equilibrium with a continuous flow. This means the gas concen-
tration in the food increases while gas partial pressure or concen-
tration in the headspace is maintained constant and equal to that

C 2014 Institute of Food Technologists®
O2 and CO2 solubility and diffusivity . . .

Figure 5–Fraction of dissolved carbon dioxide, carbonic acid, bicarbonate, and carbonate in water, as a function of pH (adapted from Daniels and
others 1985).

which the user has defined. This experimental set–up guarantees
the saturation of the food product at the initial partial pressure.
Both are used in the literature. For example, Fabiano and others
(2000) used a batch set–up that implies the samples were placed
inside a closed chamber at a constant temperature filled with a
gas mixture, whereas Ke and Ackman (1973) used a flow of air to
saturate oils with O2 .
Solubility acquisition for solid food
The second step after equilibrium is the quantification of
O2 /CO2 dissolved into food using a direct assay of the food or an
indirect measurement by measuring the O2 /CO2 partial pressure
in the headspace that is in equilibrium with the food.
Among the list of O2 quantification methods available and listed
above only a few were implemented in an experimental set–up
used to obtain O2 solubility in solid food (Figure 1): lumines-
cence detection was used in a viscous matrix (vegetable puree)
(Samapundo and others 2011), a manometric set–up was used
with lard (Davidson and others 1952) and a polarographic method
with freeze–dried food (Sidwell and others 1962). All of the O2
solubility methods for solid food are indirect measurements.
As regards CO2 , for solid matrices only indirect measurements
of CO2 were implemented in an experimental set-up for solubil-
ity measurement. Among all methodologies listed in Table 1 for
quantifying CO2 , most of them have been used in a dedicated
experimental set-up to quantify CO2 in solid food. However, the
complexity of their implementation for CO2 quantification in
solid food depends on the method as shown in Table 1. Examples
of solid food or nonfood matrices investigated are given in the last
column of Table 1.
Whatever the gas considered, for solid matrices, indirect meth- crystal microbalance (Phelps Electronics) at 40◦ C, in 10 different polymers;
ods are the most commonly used and, in this case, measurement Wong and others (1998) used a Cahn electronic microbalance at temperatures
of O2 /CO2 is generally achieved via the quantification of the ranging from 120 to 300◦ C in 3 different polymers.
O2 /CO2 partial pressure in the gas phase in contact with the
product after a desorption step to extract O2 /CO2 content. How-
ever, implementation of the set–up with direct measurements of
O2 /CO2 content is possible with the gravimetry method.
Solubility measurement based on a direct quantification of
gases. Gaseous solubility with gravimetric apparatus is easy to
handle. The food sample is enclosed in a hermetic chamber, on
a support, that relies on high–precision mass balance. It is nec-
essary to totally desorb the O2 /CO2 initially contained in the
sample (under vacuum or by nitrogen flow); and then the sam-
ple is submitted to O2 or CO2 flow until equilibrium (constant
mass).The perfectly controlled conditions of humidity, tempera-
ture, and O2 /CO2 partial pressure in the surrounding medium of
the product is required to obtain an accurate measurement. Gen-
erally, the use of the gravimetry method to measure O2 variation
in food products has been made to assess the antioxidant capac-
ity of oils (Pénicaud and others 2010). Most of the references of
gravimetric measurements for CO2 solubility are for membranes
which are either bio–based, such as wheat gluten films (Pochat-
Bohatier and others 2006) or synthetics (Aubert 1998; Wong and
others 1998).1 Indeed, among the 120 values of CO2 solubility
measured in common synthetic polymers listed in the review of
Tomasko and others (2003), the majority of data (around 100
values) were obtained by gravimetry, confirming the prevalence
of this methodology in the fields of polymer studies and mem-
brane science. Few measurements have been carried out on food
matrices, for example, on CO2 solubility in olive oil (Yokozeki
and Shiflett 2011). Some bias could be introduced due to the
1 Aubert (1998) uses a specific gravimetric/piezoelectric method, with quartz


C 2014 Institute of Food Technologists® Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 273
O2 and CO2 solubility and diffusivity . . .
loss of volatiles by the sample (if the desorption step is made by
using vacuum) and/or due to buoyancy. Therefore, some correc-
tions should be performed. Moreover, it appears very difficult to
manage O2 /CO2 sorption measurement in wet samples because
controlling humidity usually generates some variations in the mass
of the sample that add too much noise to the O2 /CO2 sorption
kinetic leading to too high uncertainty on the measured solubility,
especially when materials sorb low amounts of O2 /CO2 . These
main drawbacks explain why the gravimetric method is widely
used in the study of solubility in polymers and not yet in food
matrices.
Few direct methods exist to quantify O2 /CO2 (section “Direct
measurements of O2 /CO2 ”), and more difficulties exist to im-
plement them to obtain O2 /CO2 solubility in solid food, mainly
due to the nonhomogeneity of solid matrices. Experimental set–
up essentially used indirect methodologies to quantify O2 /CO2
solubility.
Solubility measurement based on indirect quantification of
gases. In food fields, the experimental set–up generally used to
assess and calculate the solubility value at partial pressure is the
static method (section “Equilibrium set–up”). This is typically
used by indirect methodologies to obtain solubility, through the
monitoring of changes in pressure or volume of the headspace
(that is, the manometric method by Sivertsvik and others (2004a))
or partial pressure directly with noninvasive measurement (that is,
Li and others 2008). Among all the data found in the literature,
some of them presented solubility values that measured using de-
vices such as the Clark electrode or O2 /CO2 luminescence–based
sensors immersed in the liquid. Knowing that these devices mea-
sure only partial pressure and that their internal calibration is based
on Henry’s coefficient for water, the quantification done was not
strictly speaking a solubility value but was equivalent to a measure
of solubility in water!
Quantification methods commonly used to assess solubility in
solid food are (a) chromatography–based and infrared–based ones
to assess changes in partial pressure/concentration of the target gas
(O2 /CO2 ) in the headspace, (b) manometric or volumetric meth-
ods to assess change in total pressure or volume in the headspace.
One additional indirect methodology for solid food products is (c)
a quantification of gas after entrapment by a scavenger, generally a
chemical assay and considered as a direct method for liquid, namely
chemical titration for CO2 (Gill 1988) or polarographic method
for O2 (Sidwell and others 1962). In this latter case, assessment
could be done directly in the scavenging phase using a pH–based
electrode. For example, Wang and Ogrydziak (1986) extracted
CO2 from fish flesh after blending of the sample in an acidic buffer
solution, and the measured CO2 directly in the liquid phase using
a pHelectrode. Other indirect methods are referenced for CO2
in Table 1; nevertheless, the most used methodologies are among
the above–mentioned list. For O2 , the use of (d) luminescence–
based methods is a promising way to obtain data of O2
solubility.
Chromatography/infrared headspace method. Chromatogra-
phy and infra–red measurement could both be used to mea-
sure a variation of gaseous concentration of headspace at the
gaseous solubility determination in food. The set–up is easy to
handle, it could be, for example, a hermetic jar with volume
and pressure controlled such as that used with the respiration
measurement of vegetables (Guillaume and others 2010). The
major use of chromatography was a quantification of O2 /CO2
extracted from saturated food matrices, such as Girard and Boy-
aval (1994) and Pauchard and others (1980) measured CO2 con-
274 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014
tained in cheese after release of gas. However, like the chromato-
graphic method, an infra–red set–up could be used to measure
gas absorption or release (Watten and others 2004). Both sys-
tems need a gaseous volume to quantify O2 /CO2 concentration,
and monitoring sorption or desorption could imply extraction of
volatiles.
Manometric/volumetric method. The manometric method has
been used by several researchers (Fava and Piergiovanni 1992;
Piergiovanni and Fava 1992) who measured the solubility CO2 in
about 20 food matrices such as raw and cooked meats, cheese, and
pasta (Figure 2a and b). More recently, using the same method-
ology, Fabiano and others (2000) analyzed the CO2 content in
pesto sauce. Sivertsvik and co–authors measured CO2 solubility
in 5 different fishes (Sivertsvik and others 2004b) and meat (ham
and 2 types of sausage) (Sivertsvik and Jensen 2005). For O2 solu-
bility, this determination in olive oil used the manometric method
(Davidson and others 1952; Rodnight 1954). It seems to be a
bit trickier to monitor volume change while maintaining con-
stant pressure than to detect pressure change while maintaining
constant volume in a rigid container. Indeed, just 1 volumetric
determination was found (Rotabakk and others 2007) and the
authors reported CO2 solubility in chicken by measuring the vol-
ume change of flexible pouches (Figure 2a). Gaseous release or
absorption could be measured.
Chemical titration. After gaseous absorption, the O2 /CO2 des-
orbed from the food matrices by acidic solution is trapped in and
reacted with a scavenger (mainly liquid–based), which is then
assayed, most of the time by chemical titration. With the mano-
metric methods, chemical titration is one of the most preferred
methodologies to quantify CO2 in solid food: see, for example,
the work of Gill (1988) and Jakobsen and others (2004, 2009).
Chemical O2 quantification by the Winkler test is possible in
aqueous solution, but with solid food it is difficult, essentially due
to multiple components that can react with the chemical additive
used for the assay (that is, iodine).
Among all existing techniques (Table 1), chemical titration of
CO2 scavengers appears currently the most versatile and low–cost
one to determine CO2 solubility for any kind of product (liquid
or solid); but does not permit on–line measurements because it is
destructive, with a step of desorbing and trapping CO2 that could
exceed 24 hours depending on the nature of the sample (liquid or
solid).
Different scavengers can be used: Ba(OH)2 for solids, such
as for meat (Gill 1988) or KOH and NaOH for liquids, such
as for wine, AOAC 28.1.46 (Horwitz and Latimer 2005). In
soil science, NaOH and Ca(OH)2 are commonly used to mea-
sure CO2 production by solid matrices, according to a soda–
lime method (Keith and Wong 2006). The author both used
Ba(OH)2 solution (in excess) which reacts with gaseous CO2 to
form barium carbonate (BaCO3 ), a solid compound. The CO2 is
being consumed by Ba(OH)2 , the overall equilibrium of the re-
action encourages the release of CO2 content into the matrices
until no CO2 remains in the sample. The residual quantity of
Ba(OH)2 is then titrated against a standard hydrochloric acid so-
lution (HCl). Ba(OH)2 solution (in excess) reacts with gaseous
CO2 to form BaCO3 . An example of a possible experimen-
tal set–up for performing such experiment is given in Figure 6.
Furthermore, the accuracy of titrimetric methods is not well as-
sessed. Some authors criticized its inaccuracy (coefficient of vari-
ation around 10%) (Girard and Boyaval 1994), whereas other au-
thors disagreed (coefficient of variation around 4%) (Keener and
others 2001).

C 2014 Institute of Food Technologists®
O2 and CO2 solubility and diffusivity . . .
Figure 6–Example of experimental set-up to measure carbon dioxide content in liquid or solid food, and associated reactions (adapted from Gill 1988).
Oxygen luminescence sensors. According to the review of
Pénicaud and others (2012), the use of indirect luminescence–
based methods for measuring O2 content and O2 transfer in solid
food matrices is the most promising way to obtain data of O2
solubility and diffusivity coefficients. They permitted the devel-
opment of nondestructive methods which have been used with
various matrices (foods, polymers, human tissues, and so on) for
monitoring O2 profiles in the headspace of packed food (Smiddy
and others 2002a, b; O’Mahony and others 2006; Hempel and
others 2013), for determining O2 permeability of polymers and
packaging materials (Siró and others 2010; Diéval and others
2011), for in situ measuring O2 level and diffusion of O2 in hu-
man cellular tissues (Nock and others 2009; Nock and Blaikie
2010), for characterization of O2 sorption in film polymer (Li and
others 2008, 2011), and for assessment of O2 dissolved in foods
(Smiddy and others 2002b; Nevares and others 2010; Pénicaud
and others 2010). However, the main bottleneck in measuring O2
solubility is the almost inevitable O2 consumption by the food
that can occur due to (a) microorganism respiration, (b) chemical
reactions such as oxidation, and/or (c) metabolism of the prod-
uct itself (in the case of respiring products). The experimental
set–ups used for measuring O2 solubility and diffusivity should
take into consideration these constraints (section “Interfering
reactions”).
Implementation of the aforementioned method is easier in liq-
uids than in solids. To date, only 2 values of O2 solubility in
“dense” matrices with luminescence probe are known from Sama-
pundo and others (2011) on potato and potato–spinach puree
(Figure 1). However, these values are questionable because this
methodology enables to quantify O2 partial pressure in media, not
a concentration, even if a conversion is made with O2 solubility
in water.
The listing of the different methodologies currently used for
assessing dissolved O2 /CO2 concentration in solid matrices re-
veals a strong lack of nondestructive and/or noninvasive O2 /CO2
methods (Table 1). Development of sensors able to react with
gaseous O2 /CO2 and/or dissolved O2 /CO2 would be essential
to achieve a significant breakthrough in the domain of food en-

C 2014 Institute of Food Technologists®
gineering for the measurement of O2 /CO2 solubility and further
diffusivity.
Finally, we note that the gaseous sorption or desorption in ma-
trices of food may last for minutes, hours, or days (in the case of
a big sample for example) and it is possible that thermodynamic
equilibrium is not reached in the time scale of food shelf–life
(Keller and Staudt 2005). The implementation of methodologies
to obtain these data must take into account such slow kinetics
and the biases that may appear during the time of the experiment
(discussed later on in sections “Interfering reactions” and “Fac-
tors Impacting and Predictive Modeling of Oxygen and Carbon
Dioxide Solubility”).
Typical values of O2 /CO2 solubility in solid food
The main difficulty with comparing O2 /CO2 solubility values
in food is the variety of units that are found in the literature. For
example, some publications used the Ostwald coefficient (ratio of
the volume of gas absorbed per unit volume of the solvent) or the
Bunsen coefficient (volume of gas reduced to 0 ◦ C and to 1 atm ab-
sorbed by unit volume of solvent at a gas partial pressure of 1 atm).
To employ units from the Intl. System of Units (mol.kg–1 .Pa–1 ),
assumptions must be made, essentially on the density of the fluids
(liquid or gas phases). Sometimes, gaseous partial pressure imposed
at the sample is not indicated and, according to the methodological
details, we assume generally an atmospheric concentration for O2 ,
or 100% of CO2 . These exhaustive databases for solid products
(Figure 1, 2a, and 2b, but also 3 and 4) could allow comparing all
of the values existing in the literature, and also methodologies.
Analysis of the data in the literature (Figure 1) shows that O2 sol-
ubility varied between 8.8×10–10 mol.kg–1 .Pa–1 (obtained for pre-
cooked freeze–dried chicken at 20 ◦ C (Sidwell and others 1962))
and 1.1×10–7 mol.kg–1 .Pa–1 (for sunflower oil at 20 ◦ C). It de-
pends on the temperature (for example, for water, at 0 ◦ C; sol-
ubility is 2.3×10–8 mol.kg–1 .Pa–1 while it decreases to 9.8×10–9
mol.kg–1 .Pa–1 at 50 ◦ C (Battino and Clever 1966)); but also on
the composition of the product: at 20 ◦ C, O2 solubility in wa-
ter is 1.4×10–8 mol.kg–1 .Pa–1 (Battino and Clever 1966), while it
is 5.3×10–8 mol.kg–1 .Pa–1 in herring oil (Ke and Ackman 1973),
Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 275
O2 and CO2 solubility and diffusivity . . .
or 5.4×10–9 mol.kg–1 .Pa–1 in freeze–dried chicken, uncooked, 0%
relative humidity (Sidwell and others 1962). Furthermore, we note
O2 was found to be more soluble in olive oil and sunflower oil than
in water, respectively, 5.4 and 7.9 times more soluble at 20 ◦ C, this
can be explained with the lower affinity of oxygen molecules for
polar products (water) than for nonpolar products (oils) (Pénicaud
and others 2010).
As already mentioned, CO2 solubility has been more studied
than O2 and, consequently, more data are available in the lit-
erature. We separated the data collected in 2 figures: Figure 2a
representing CO2 solubility in high–water content food, and Fig-
ure 2b in high–fat-content food. In all of there solid matrices,
CO2 solubility was found to vary between 4.9×10–8 for grated
parmesan cheese at 7 ◦ C to 7.8×10–7 mol.kg–1 .Pa–1 for a snel-
lina cheese at 7 ◦ C (Fava and Piergiovanni 1992). Analysis of data
gathered in Figure 2a and b did not reveal any impact of the na-
ture of the food on this coefficient. For example, CO2 solubility
varies from 1.8×10–7 to 3.7×10–7 mol.kg–1 .Pa–1 for a pasta type
product at 7 ◦ C (Fava and Piergiovanni 1992), from 2.5×10–7
to 5.5×10–7 mol.kg–1 .Pa–1 for a meat product with temperature
4.9×10–8 to 3.6×10–7 mol.kg–1 .Pa–1 for cheese products (Fava
and Piergiovanni 1992; Jakobsen and Jensen 2009). However, as
for O2 , CO2 solubility was found higher in fat products than in
aqueous ones: at 22 ◦ C, CO2 solubility was found, respectively,
1.6 and 1.8 times more soluble in olive oil and grape seed oil
than in water (Pauchard and others 1980). We note that, in water,
values of CO2 solubility are around 25 times higher than that of
O2 at 25 ◦ C (Carroll and others 1991; Geankoplis 1993); and 10
times higher at 25 ◦ C in fat products (olive oil), which means that
the solubilization of CO2 would be more visible than that of O2 .
Interfering reactions
In addition to gas solubilization, real food products are subjected
to complex and kinetic reactions (biological or chemical) in which
either O2 or CO2 is consumed or released, which is not the case
(or to a lesser extent) in water and polymeric membranes. Acqui-
sition of the true solubility coefficient (the same for diffusivity)
is difficult and most of the time values reported for real foods
refer to an apparent solubility coefficient (and an apparent diffu-
sivity) but are not indicated as such. Indeed, steady state condition
for solubility determination takes a longer time when these reac-
tions occur and in addition is considered as a pseudo–equilibrium
state. For instance, neglecting gas consumption (for example, O2 ),
the solubility coefficient (SA ) is usually overestimated during the
experiment (Eq. 1). The next section will present the main inter-
fering kinetics reactions through illustrations and the ways, when
possible, to overcome then and tentatively assess true solubility.
Food metabolism. Aerobic respiration is the common metabolic
pathway for most living organisms to provide sufficient energy to
maintain their cellular integrity. This oxidation process requires O2
to degrade glucose and it produces CO2 . It is widely studied in
fresh and fresh–cut fruits and vegetables because of its importance
in MAP: it interplays with gas transfers through the packaging
to permit the establishment of a steady atmosphere. The respira-
tory activity is determined either by monitoring O2 consumption
or CO2 production, and modeled by using Michaelis–Menten–
type equations, considering, or not, the possible CO2 inhibition
on product respiration (Fonseca and others 2002). Whatever the
method used to determine this activity, it relies on a global assess-
ment including, of course, cells’ respiration but also skin resistance
to gas transfer, gas solubility, and gas diffusivity in the product.
In addition, this global assessment also takes into account the res-
276 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014
piration of microorganisms, when fresh fruits and vegetables are
contaminated (which is commonly the case for those produced in
fields). Then to obtain true values of O2 /CO2 solubility in fruits
and vegetables, respiratory activity in both fresh food and microor-
ganisms must be stopped. This could be done by using preserva-
tion treatments commonly encountered in various food industries
(for example, thermal, alcohol conservation) and sanitation pro-
cedure (UV exposition or chlorine treatment) respectively. But,
preservation treatments would certainly lead to textural/chemical
changes in the core of the food and consequently modify the prod-
uct. As a consequence they are never applied to fresh fruits and
vegetables and it is still a tricky task to manage product respira-
tion while measuring O2 /CO2 solubilities. Regarding sanitation,
textural and chemical changes might also occur but remain at the
surface of the food; then such procedures are commonly applied
prior to the determination of respiration in fresh fruits and veg-
etables. Despite the difficulty to directly measure gas solubility
(and diffusivity) in such products, their estimation would be pos-
sible from global respiration measurement, if cell respiration and
skin resistance were accurately characterized and a mass balance
formalism established for gas exchange in the fresh and sanitized
produce (cell respiration, skin resistance to gas transfer, gas solu-
bility, and gas diffusivity) (Fonseca and others 2002). Respiration
also exists in “nonrespiring” products, but not as pronounced as in
fresh fruits and vegetables. It relies on the cell activity (mitochon-
drial consumption of O2 ) in postmortem muscle (Zhao and others
1994). This respiration rate of meat is turned into an asset in the
case of vacuum–packing where residual O2 is then consumed by
the product, and it eventually increases the CO2 concentration in-
side, a function of the choice of permeability properties of the film
(Blakistone 1999). However, the amount of O2 consumption and
CO2 production by meat respiration is neither well known nor
quantifiable. Few studies exists, for example, Gašperlin and others
(2001) estimated the O2 consumed at 6.34 m%O2 .g–1 food .h–1 for
meat (in the case of raw meat) and 3.50 m%O2 .g–1 food .h–1 for
heated meat (at 60 ◦ C). The authors overestimated the values of
mitochondrial respiration because they did not take into account
the consumption due to oxidation and to microbial metabolism.
In the case of heated meat where we can suppose that microor-
ganisms and mitochondrial respiration were both inhibited, the
amount 3.50 m%O2 .g–1 food .h–1 could represent O2 consumption
due to oxidation. Meat respiration is essentially due to high respi-
ratory activity of the mitochondria contained in meat cells (Kim
and others 2011), which decreases with time. An assumption could
be made with consumption and production of both these gases by
cells, especially by mitochondrial metabolism, more easily acces-
sible in vitro. It is possible to characterize meat tissue O2 rate
consumption after isolation of the mitochondria (Gao and others
2013). Even if respiration parameters are accurately determined,
there is still an uncertainty about them. This uncertainty of the
solubility value is amplified by a correction applied to the amount
of sorbed O2 /CO2 measured in the product to calculate the O2
and CO2 quantity due to solubilization.
Oxidant capacities. Beyond the aforementioned variability in
O2 solubility induced by the presence of fat and/or protein, O2
is also very reactive with unsaturated fat and proteins. Oxidation
reactions induce O2 consumption that disturbs the solubility mea-
surement (overestimation of the “true” solubility). Unfortunately,
it is very difficult at this moment in time to assess O2 consumption
for 1 mole or 1 g of fat or protein due to the complexity of ox-
idation and oxygenation mechanisms, and then little information
is found in the literature. In the past, Frayn (1983) has studied fat

C 2014 Institute of Food Technologists®
O2 and CO2 solubility and diffusivity . . .
and protein oxidation reactions in vivo, using a global approach
focusing on O2 consumption and CO2 production during the res-
piration phenomena. According to his results, protein oxidation
would lead to the consumption of 0.04 mol of O2 and the produc-
tion of 0.03 mol of CO2 per gram of protein. For fat, one gram
of a studied fat (PSOG C55 H104 O6 ) would consume 0.09 mol of
O2 . However, to our knowledge, there is no equivalent study to
quantify O2 consumption due to the fat or protein oxidation in
other food products. Most of the studies focused on the oxidation
mechanism and oxidation rate. Evaluation of O2 consumption by
fat and protein oxidation on the basis of a mechanistic analysis is
very tricky. Indeed, oxidation of lipids and proteins is complex
with the occurrence of a chain reaction where the role of O2 is
not always well understood. For instance, more than 90 different
reactions were listed by Roman (2012) in her study on oil oxi-
dation during thermal treatment. O2 takes part in only a few of
them, generally in the propagation step of oxidation (Roman and
others 2013).
Oxidation rates of fat and protein are compatible with the
time scale of solubility measurement (around 24/48 h to obtain
equilibrium in food). For instance, kinetic rates of oxidation by
singlet oxygen are around 0.5 and 1.5 .105 L.mol–1 .s–1 for fat
and around 1.3 and 5.107 L.mol–1 .s–1 for amino acid (Choe and
Min 2005). To compare these kinetic rates, the half–life time is
commonly used, which is the time required to divide the initial
concentration by 2 (Eq. 4).
1 time span of the experiment is long enough to be significantly
t 12 = (4)
k × [B]0
For one mole of product, oxidation of amino acids occurs faster
than lipid oxidation. Obviously, in real food, lipid and protein
oxidation kinetics depend on the content of each molecule: for
example, in the case of a product with a high lipid content (>30%)
and 10% protein (as in liver pâtés) lipid oxidation was faster than
protein oxidation, but in minced cod muscle, with low lipid con-
tent of 0.6%, protein oxidation occurs faster than lipid oxidation
(Lund 2007).
In the case of raw meat products, O2 can react, for example,
with myoglobin to produce metmyoglobin, a reaction responsible
for color changes during storage (Eq. 5) (George and Stratmann
1952; Sáenz and others 2008).
Mb 2+ + O2 ↔ Mb O22+ (5)
According to Eq. 5, 1 mole of myoglobin would react with
1 mole of O2 . Considering a myoglobin concentration of
486 mg.100 g–1 as found by Babji and Abdullah (1998) in beef,
0.0285 mmol of myoglobin would react with the same quantity of
O2 . Considering only the myoglobin reaction, 100 g of beef would
consume around 0.9 mg of O2 , which is far from being negligible.
Indeed, starting from the value of O2 solubility found in water at
20 ◦ C (around 0.8 mg O2 per 100 g, Figure 1), the consumption
of O2 by myoglobin would be equivalent to the quantity of O2
dissolved in the 100 g of product at equilibrium with atmospheric
O2 pressure. Let us now consider the total protein content in a
sample of meat (20 wt%, around 40–fold more than myoglobin
(Babji and others 1989). It is obvious that total O2 consumption
due to oxidation of proteins would overcome the O2 solubility
value. Furthermore, in addition to proteins, food products may
contain different antioxidant components, such as vitamin C or E,
carotenoids, polyphenols, or enzymes like catalase, which inter-

C 2014 Institute of Food Technologists® Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 277
act with O2 dissolved in food. As for protein, the determination
of O2 consumption by antioxidants is not a sinecure, mainly due
to the complexity of oxidation mechanisms and the necessity to
have recourse to simplified equations of reaction to determine the
number of moles of O2 that react with one mole of antioxidant.
It is thus very difficult to take into account oxidation reactions
while measuring O2 solubilities and to make some corrections of
the measured amount to retrieve the “true” solubility. A solution
to overcome this difficulty would be to correlate the O2 con-
sumption to the total antioxidant capacities of the food product
studied. These antioxidant capacities are indeed more easily as-
sessed by experimental measurement than the oxidation reaction
rate (Pérez-Jiménez and others 2008; Serpen and others 2012).
This was never attempted but could be a good future research
path. In any case this future research should pay attention to the
natural variability in antioxidant content within different classes of
product.
Microbial metabolism. The microbial population of a food
product can affect O2 and CO2 concentration due to the res-
piration metabolism of aerobic microorganisms. This effect is usu-
ally observed in the monitoring of headspace gas concentration
of packed food. For anaerobic microorganisms, CO2 production
could also be significant, such as, for example, production of CO2
by yeast or fermentative bacteria (Eliot and others 2006). Aero-
bic or anaerobic respiration of microorganisms could both occur
during the measurement experiments of CO2 or O2 solubility if
no precautionary measure for avoiding this is taken. Indeed, the
affected by the microbial respiration. According to the few publi-
cations that have focused on the quantification of microorganism
respiration in real food/packaging systems (only 2 papers were
found in the literature dealing with the respiration of Pseudomonas
(Thiele and others 2006) and O2 /CO2 consumption/production
by a consortium of bacteria (Simpson and others 2001a). This phe-
nomenon is not negligible for microbial counts above a threshold
value. Indeed, Simpson and others (2001a) have demonstrated
(theoretical and experimental work) that for microorganism con-
centrations more than 105 CFU.g–1 , headspace gas composition
was substantially modified and could reach an anaerobic medium
in a short time (less than 3 d). This phenomenon would be even
more amplified if the oxidation rates of reactions overlaid with the
microorganisms’ respiration were higher than 10–6 s–1 (Simpson
and others 2001a). In spite of this preliminary work that revealed
that microorganism respiration would be far from being negligi-
ble, O2 /CO2 consumption/production due to microbial reactions
is still neglected when measuring O2 /CO2 solubility coefficients.
Therefore, this O2 /CO2 solubility values measured by these au-
thors could be distorted by microorganism respiration. However,
microorganism growth could be avoided by ultraviolet exposure or
adding an antimicrobial compound such as sodium azide, ethanol,
sorbic acid, and so on (Sanches Silva and others 2007; Pénicaud
and others 2011).
Factors Impacting and Predictive Modeling of Oxygen
and Carbon Dioxide Solubility
Both O2 and CO2 solubility depend on environmental factors
such as temperature or pressure and on intrinsic parameters such as
composition and structure of the matrices. Intrinsic characteristics,
such as the effect of salinity and sugar concentration on O2 solu-
bility, have been well described (Langø and others 1996; Pénicaud
and others 2012), especially for aqueous solutions. As for O2 , CO2
solubility seems deeply impacted by salt content (Schumpe 1993)
O2 and CO2 solubility and diffusivity . . .
and its effect has been well documented for NaCl in the liter-
ature (Duan and Sun 2003; Portier and Rochelle 2005). Some
parameters have an impact on both O2 and CO2 solubility, oth-
ers have a specific action on one gaseous species. Fat and protein
contents seemed to greatly impact both O2 and CO2 solubilities,
especially because O2 and CO2 are classically more soluble in a fat
than in an aqueous phase. In addition, in the specific case of O2 ,
it is consumed by oxidation reactions that could deeply disturb
the measurement of O2 solubility (section “Oxidant capacities”).
Finally, in the case of CO2 solubility, as easily deduced from Eq. 3,
the pH value of the matrices has been noticed as a particularly
relevant parameter affecting CO2 dissolution (Zeng 1995).
In the following, the impact of these main parameters on gas
solubility will be considered with special emphasis on current
bottlenecks in the knowledge of the relationship between food
nature/structure and the value of solubility. Mathematical mod-
eling approaches to predict gas solubilities in food will then be
addressed.
Temperature
The solubility of O2 and CO2 decreases when the temperature
increases according to a van’t Hoff–type expression (Eq. 6).
 
−Hs
S A = S0 exp (6)
RT
where S0 is the preexponential factor, HS is the apparent heat
of sorption (or enthalpy of sorption, enthalpy of solubilization, or
calorimetric enthalpy), R is the universal gas constant, and T is the
absolute temperature. However, the main problem with using this
expression is to access to the value of enthalpy. This value includes
the heat of dissolution, condensation, and mixing in the phase. It is
well known for water and other aqueous solutions; for instance, the
enthalpy of sorption HS for O2 was found to be equal to –18.4
and –15.1 kJ.mol–1 in distilled water and NaCl solution (0.5 M) at
15 ◦ C, respectively (Mirhej 1962). O2 solubility in wine would be
affected by temperature in the same manner as in water (Chiciuc
2010). For CO2 the enthalpy of sorption was found to be equal to
–19.4 kJ.mol–1 in water (Carroll and others 1991). On the basis of
the aforementioned values obtained in aqueous solutions and using
a mixing law, Simpson and others (2004) estimated the enthalpy
of gas sorption in gelatin to be –13.2 kJ.mol–1 for O2 and –19.7
kJ.mol–1 for CO2 , pointing out that the temperature would have
a similar effect on O2 and CO2 dissolution. If no experimental
values of enthalpy for O2 and CO2 sorption in real food products
were reported in the current literature, it is nevertheless possible
to estimate it, by taking the gas solubility value assessed at various
temperatures (Figure 2) as input data for Eq. 6. For instance, from
CO2 solubility values measured by Sivertsvik and Jensen (2005)
and Jakobsen and Jensen (2009a), the enthalpy for CO2 sorption
was estimated in the present work to be between –16.25 kJ.mol–1
and –12.73 kJ.mol–1 in cheese (for temperatures ranging from 0
to 25 ◦ C) and between –13.76 kJ.mol–1 and –12.37 kJ.mol–1 in
meat (for temperatures ranging from 0 to 8 ◦ C). Such estimated
values are very close to those measured in water. For comparison,
the enthalpy of O2 sorption was experimentally found to be equal
to –31.6 kJ.mol–1 , and enthalpy of CO2 sorption to be –13.7
and –17.7 kJ.mol–1 in hybrids of poly(amide–6–b–ethylene oxide)
(Kim and Lee 2001). From literature values and values calculated
in this work, it is obvious that enthalpy of sorption is around –
20kJ.mol–1 , whatever the product considered. As a consequence,
278 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014
solubility values would decrease by 2 orders of magnitude when
the temperature increases from 0 to 20 ◦ C.
Other models exist to predict O2 and CO2 solubility as a func-
tion of temperature. For example, Carroll and others (1991) used
an empirical model to predict CO2 solubility as a function of
temperature, based on a simple extension of Henry’s law model,
valid from 0 to 160 ◦ C. Generally, these empirical models often
couple the effect of temperature to that of salt or sugar addition.
The most famous ones are the equation of Benson and Krause
(1984), that relates the effect of temperature and salt content to
O2 solubility using a polynomial relationship, and that of Sadler
and others (1988) that allows to estimate O2 solubility in fruit
juices according to a linear law including temperature and ◦ Brix
(in the range of 4 to 40 ◦ C).
An analysis of O2 solubility data against temperature allows
to point out that in fish oil an unaccounted atypical profile was
obtained (Figure 1): solubility increased with increasing the tem-
perature to 40 to 60 ◦ C, and then fell when the temperature was
raised to 80 ◦ C. The same atypical profile was obtained for CO2
solubility in the fat tissue of meat (Figure 2b): it increased with
temperature until a maximal value was reached at 10, 14, and
22 ◦ C for fat tissue of lamb, pork, and beef, respectively, and then
decreased at higher temperatures (Gill 1988). This unexpected be-
havior in relation to the temperature (“bell–like curve”) was more
related to a possible antagonistic effect between temperature and
viscosity: increasing temperature decreases viscosity which should
favors gas diffusion and then solubilization but at the same time
increasing temperature directly decreases solubilization (van’t Hoff
law) (Ke and Ackman 1973). A lack of knowledge still remains
today about the impact of temperature on O2 and CO2 solubility
in food products.
Salt and sugar content
The solubility of O2 and CO2 in aqueous salt solutions usually
decreases when the salt concentration increases. This impact of
salinity and sugar content on O2 solubility has already been re-
viewed by Battino (1981) and recently completed by Geng and
Duan (2010). The effect of salinity was usually coupled with that
of temperature. For high salinity values, the temperature effect
on O2 and CO2 solubility is extremely small (Millero and Huang
2003; Debelius and others 2009; Verberk and others 2011). The
variation of O2 solubility by adding salt was correlated to the na-
ture of the salt: for example, addition of 1 mol.kg–1 of NaCl leads
to a decrease in O2 solubility of 26%. This decrease is 38% with
MgCl2 , 51% with MgSO4 , and 53% with Na2 SO4 (Millero and
others 2002). In the case of CO2 solubility, the addition of salt has
less impact than on O2 solubility: for example, the addition of 1
mol.kg–1 of NaCl decreased the CO2 solubility 14% (Duan and
Sun 2003).
Similar to salt, increasing sugar concentration tends to decrease
O2 solubility in food, with a decrease in magnitude which de-
pends on the nature of the sugar (and more specifically on its
carbon number). For example, the addition of 1 mol.kg–1 of ri-
bose caused a decrease in O2 solubility of 24%, this decrease was
of 29% with glucose, 38% with maltose, and 47% with raffinose
(Mishima and others 1996, 1997). Sugar alcohols, such as mannitol
or sorbitol, have the same effect as sugars on O2 solubility (Whit-
combe and others 2005). In the same way, but to a lesser extent,
CO2 solubility decreases with increasing sugar concentration. This
effect also depends on the nature of the sugar: the addition of 1
mol.kg–1 of glycerol caused a decrease in CO2 solubility of 7% and

C 2014 Institute of Food Technologists®
O2 and CO2 solubility and diffusivity . . .
0.8 mol.kg–1 of glucose or sucrose to a decrease of 15% (Risch-
bieter and others 1996). The impact of salt and sugar addition on
O2 /CO2 solubility in real food products is less referenced than for
aqueous solutions and not at all, to our knowledge, in solid food
matrices.
Some mathematical modeling has been attempted in order to
predict O2 solubility in aqueous–based media according to their
salt and sugar composition. In addition to the empirical correla-
tions of Benson and Krause (1984) and Sadler and others (1988)
(see above), Schumpe and others (1982) predicted O2 solubility
by taking into account the contribution of each ion species dis-
solved in the solution using a semiempirical UNIFAC model to
calculate the chemical acitivity of each species present. Gros and
others (1999) went further than Schumpe and others (1982) by
considering, in addition to salt, the activity of each functional
group of macromolecules on O2 and CO2 solubility. Ji and oth-
ers (2007) proposed to use an equation derived from statistics-
associated fluid theory (SAFT; Economou 2002) to predict the
effect of sugar content (glucose, fructose, sucrose, and maltose)
on O2 solubility in liquids by taking into account molecular
interactions.
pH (for CO2 solubility)
Gaseous CO2 dissolves in a liquid phase and then dissociates
into various dissolved species according to Eq. 3. This dissocia-
tion depends on the pH of the liquid phase (Figure 5). Therefore,
the pH of a food matrix strongly effects the quantity of CO2
able to dissolve within. For instance, CO2 absorption by a buffer
solution at pH 5.5 is lower than that by water (pH 7) because
the hydration reaction (CO2 which turns into HCO3 – ) is higher
at pH 7 than pH 5.5 (Lı́vanský 1982). In real food products,
the same effect of initial food pH on the quantity of CO2 able
to dissolve in the product was noticed (Gill 1988; Jakobsen and
Bertelsen 2004). Therefore, decreasing the pH value leads to a
decrease in CO2 solubility (less CO2 is able to dissolve in the
product) and increasing the pH–value leads to an increase in CO2
solubility. For example, Gill (1988) found that for pH increasing
linearly from 5.4 to 6.9, CO2 solubility increased approximately by
1.5×10–7 mol.kg–1 .Pa–1 for each pH unit increase. However, such
behavior was not confirmed with fish products (Sivertsvik and
others 2004b). It is worth noticing that in all the aforementioned
studies, only the initial pH in the food matrices was measured
and not its evolution as a function of time and CO2 dissolution.
However, it is fair to say that CO2 dissolution leads to pH changes
to a greater or lesser extent depending on the buffer properties
of the food. To be as rigorous as possible, the addition of CO2
into a matrix must be considered from the acidification point of
view: when CO2 dissolves, it acts as an acid on the pH value. A
theoretical mathematical approach exists to model the effect of pH
on CO2 transfer rate in liquids and vice versa (Shanableh 2009).
In this work, the amount of CO2 is represented by the concen-
tration of all its species present in the solution (CO2 , HCO3 – ,
and CO3 2– ) as a function of time. According to the authors, the
contribution of the different carbonic species on CO2 solubility
is far from negligible. However, this type of model does not ex-
ist for real food and its applicability to such complex products is
questionable. Indeed, the buffering properties of real food depend
on its composition and then would limit the versatility and ex-
trapolation of such models to other kinds of products than the
one for which it was developed. The only relationship between
pH change and CO2 solubility was the one established by Gill
and others (1988). It was an empirical relationship that could nei-

C 2014 Institute of Food Technologists® Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 279
ther be extrapolated to another pH range nor to a product other
than meat. Currently, the prediction of the effect of pH on CO2
solubility could only be assessed case by case and in an empirical
manner.
Effect of fat and protein content on O2 /CO2 solubilities
If the impact of fat and protein contents was clearly identified
on CO2 solubility, it was never clearly stated to what extent it
would affect this solubility values. For example, recently, it was
found that fat content had a low impact on CO2 solubility in
meat (Jakobsen and Bertelsen 2004), whereas it was significant for
cheese products (Jakobsen and Jensen 2009). An earlier study by
Fava and Piergiovanni (1992) described a relationship between the
solubility coefficient and food composition (including protein and
fat content) for a meat product, salami, and fresh pasta. This rela-
tionship was based on a multiple regression model relating CO2
solubility to the pH (ranging from 4.93 to 6.54), the moisture
content (between 24 and 76.8%), the water activity (ranging from
0.870 to 0.999), the protein content (7.7 to 31%), and the fat
content (0.8 to 38.9%) of the product analyzed. This statistical
model was a first step toward an understanding of the relationship
between solubility and food composition. However, experimental
validation was successful only for meat products and pasta and not
for dairy products. One explanation of this discrepancy between
theoretical and experimental values would be that, during exper-
imental measurement of CO2 solubility, the authors did not take
into account possible proteolysis, lipolysis, and microbial growth
in the food, which would have randomly influenced the amount
of CO2 absorbed by the matrices (section “Interfering reactions”).
Following this preliminary modeling attempt, Jakobsen and Jensen
(2009) developed a model to predict CO2 solubility in semi hard
cheeses based on the weight fraction of water (ww ) and fat (wf ) in
the 2–phase cheese system, temperature (T), and the CO2 solubil-
ities in, respectively, pure water (SCO2/W ) and pure fat (butterfat,
SCO2/F ) (Eq. 7)
ww × SCO2/W (T) + w f × SCO2/F (T) (7)
Equation 7 was found suitable for predicting CO2 solubility
in semihard cheeses and the range of temperature from 0 to
20 ◦ C was investigated by Jakobsen and Jensen (2009). How-
ever, the authors noted that for temperatures below 10 ◦ C, pre-
dictions made considering only the water phase in Eq. 7 were
accurate enough to predict solubility in the entire cheese. The
main drawback of this equation is that, of course, it is not extrap-
olatable to other cheese and food products than those studied by
the authors.
To our knowledge, except for the aforementioned empirical
approaches, there are no mechanistic models aimed at formalizing
the relationship between O2 /CO2 solubility values and fat content
or protein content of a product. Therefore, it is thus currently
very difficult to predict O2 /CO2 solubilities in a food product on
the basis of its composition. To overcome this lack of scientific
data, specific studies aimed at the impact of food composition on
O2 /CO2 solubilities should be undertaken.
Determination of O2 /CO2 Diffusivity
Experimental set–up of O2 /CO2 diffusivity
O2 /CO2 diffusivity is not directly measured: obtaining such in-
formation requires a set of experimental data and a mathematical
model. To obtain O2 /CO2 diffusivity, a gradient of O2 /CO2 con-
centration (or partial pressure) has to be imposed within the food
O2 and CO2 solubility and diffusivity . . .
Figure 7–Example of experimental set-up to measure O2 kinetic for diffusivity identification in liquid and viscous food products (adapted from
Pénicaud and others 2010).
and then the O2 /CO2 diffusion has to be monitored (using one of
the aforementioned methodologies for measuring O2 /CO2 par-
tial pressure or concentration). For example, calibration to obtain
CO2 concentration with FTIR–ATR is very time–consuming
(absorbance crossed with a quantitative method) but it would
detect a kinetic of dissolved CO2 in solid matrices. Experimental
set–up permits direct monitoring of CO2 content in a sample, with
an analysis of spectral band variation. In the same way, an example
of experimental design used with measurement of O2 partial pres-
sure for determining O2 diffusivity is presented in Figure 7. The
diffusivity is then identified by adjusting a mathematical model of
diffusion (mainly based on Fick’s second law) to the experimental
kinetics of O2 /CO2 transfer using an algorithm of optimization
(for example, Gauss–Newton, Levenberg–Marquardt, and so on).
Fick’s second law can be solved either analytically (Crank 1975)
or numerically, using finite difference, finite element, and finite
volume, approaches more and more used in the food applications
(Wang and Sun 2003). In both cases the geometry of the sam-
ple and the boundary conditions imposed on the sample must be
strictly controlled in order to ensure the accuracy of the mathe-
matical modeling.
We noted that in some particular cases (vegetable tissues),
O2 diffusivity was obtained using permeation measurement
(De Wild and Peppelenbos 2001; Schotsmans and others 2004;
Valleguadarrama and others 2005). In this last case, a thin sheet of
material is placed between 2 atmospheres maintained at constant
and different O2 partial pressure. After a time period, the surfaces
of the sheet come into equilibrium with the diffusing sources,
thus, developing a constant gradient of surface concentrations,
leading to steady state conditions of diffusion. This state could be
expressed for a plane sheet by Fick’s first law (Eq. 8)
∂C A
J A = −D (8)
∂x
where JA is the gaseous diffusion flux (mol.m.kg−1 .s−1 ), D is the
diffusion coefficient (m2 .s−1 ), CA is the concentration of dissolved
gas A (mol.kg−1 ), and x is the distance between the interface and
measurement point (m).
Diffusivity can be estimated by measuring the flux of the diffus-
ing gas, with known surface concentrations and thickness of the
material sheet, which can be done experimentally by using one of
280 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014
the indirect measurement methodologies listed above at different
time intervals.
Typical values of O2 /CO2 diffusivity
From 0 ◦ C to 37 ◦ C, O2 diffusivity varied from 0.2 × 10–9
m .s with agar 2%w/v (Miller and others 2003) to 53 × 10–9
2 –1
m2 .s–1 with apple (Schotsmans and others 2004) (Figure 3). If
we excluded fruit cellular tissues that probably displayed a porous
texture that enhanced O2 transfer: then the range of values for
O2 diffusivity was only from 0.2 × 10–9 m2 .s–1 with agar 2%w/v
(Miller and others 2003) to 2.9 × 10–9 m2 .s–1 with water (Grote
1967); such low variation indicates that the nature of the product
only influenced the O2 diffusivity slightly. Whatever the tem-
perature, the variation is very slight leading us to conclude that
temperature has a low impact on O2 diffusivity: O2 diffusivity is
1.7 × 10–9 m2 .s–1 on water for 10 ◦ C (Langø and others 1996),
20 ◦ C (Grote and Thews 1962), and 37 ◦ C (Lightfoot 1974). As
regards the data available (Figure 3), O2 diffusivity would be lower
in oils and fats than in aqueous products.
From 0 ◦ C to 25 ◦ C, CO2 diffusivity varied from 0.2 × 10–9
m .s with egg yolk (Fabbri and others 2011) to 151 × 10–9
2 –1
m2 .s–1 with apple (Solomos 1987) (Figure 4), and if we excluded
fruit cellular tissues, the range of variations for CO2 diffusivity
was only from 0.2 × 10–9 m2 .s–1 with egg yolk (Fabbri and others
2011) to 11 × 10–9 m2 .s–1 with sausage (Sivertsvik and Jensen
2005), whatever the food matrices. The temperature has a low
impact on CO2 diffusivity. For example, in ham, CO2 diffusivity
is 3.7 × 10–9 , 3.9 × 10–9 , and 3.8 × 10–9 m2 .s–1 , respectively, for
0, 4, and 8 ◦ C (Sivertsvik and Jensen 2005). CO2 diffusivity would
be higher in meat products than in fish products (Figure 4).
In both cases (O2 and CO2 ), the lack of available data on dif-
fusivity values for solid food matrices prevented us to estimate the
activation energy on diffusivity. In theory, the increase of tem-
perature should increase the diffusion of gases. However, Simp-
son and others (2004) estimated the activation energy in gelatin
at 20.3 kJ.mol–1 for O2 diffusivity, and 14.5 kJ.mol–1 for CO2
diffusivity, taking into account the water content of the matrix.
For comparison with another field of science, activation energy
for diffusion through polyimide membranes was 17.6 kJ.mol–1
and 16.8 kJ.mol–1 for O2 and CO2 , respectively (Lin and Chung
2001). Similar activation energies were found for diffusion through

C 2014 Institute of Food Technologists®
O2 and CO2 solubility and diffusivity . . .
Figure 8–CO2 diffusivity (m2 .s–1 ) as a function of food composition (square: water, diamond: fat, and triangle: protein fraction) taking into account
values from the literature in a range of temperatures from 0 to 8◦ C. Light color dot: data of various food products: water (Carroll and others 1991),
hake (Simpson and others 2001a), sausage and ham (Sivertsvik and Jensen 2005) and dark color dot: same data plus anglerfish, cod, salmon, tuna,
wolf-fish (Sivertsvik and others 2004).
polyurethane membrane, 28.2 kJ.mol–1 and 35.6 kJ.mol–1 for O2
and CO2 diffusion, respectively (de Sales and others 2008) and
lower values were determined for a synthetic membrane made of
poly (2-ethoxyethyl methacrylate-co-2-hydroxyethyl methacry-
lamide), 15 kJ.mol–1 and 19 kJ.mol–1 for, respectively, O2 and CO2
(Tiemblo and others 2004). For liquids, there are more data avail-
able, but too high a variability prevented us from calculating any
activation energy for O2 or CO2 diffusivity. Indeed, if we ex-
amined the set of data reported for water by Langø and others
(1996) about O2 diffusivities, and we can see that the range of
variation at 25 ◦ C (from 1.6 × 10−9 to 3.5 × 10−9 m2 .s−1 ) is
as large as that obtained for the min–max span of temperatures
studied. The same observation could be made for CO2 diffusivity
(values ranging from 1.57 × 10−9 to 2.0 × 10−9 m2 .s−1 in water
at 25 ◦ C) (Figure 3 and 4). Unver and Himmelblau (1964) have
developed an empirical model to relate diffusivity of CO2 in water
to temperature, between 6 and 65 ◦ C (Eq. 9)
DCO2 = (α + βT + γ T 2 ) × 10−9
where D is a coefficient of diffusion of CO2 (m2 .s–1 ) and α, β, and
γ are constants with values of 0.95893, 0.024161, and 0.00039813,
respectively.
Predictive models for O2 /CO2 diffusivity
An alternative to experimental determination of diffusivity is the
use of a predictive mathematical model based on the characteristics
of the food structure and composition as main inputs. For example,
to estimate O2 diffusivity in gelatin (Simpson and others 2004) and
meat (Zaritzky and Bevilacqua 1988), both teams have adapted
an empirical correlation, the Wilke–Chang equation, previously
established in another field of science (Wilke and Chang 1955).
This equation (Eq. 10) correlates diffusivity of the migrant (D) as
a function of the viscosity (μ) and the absolute temperature (T).
D×μ
= constant
T
It was valuable initially for infinite dilute solution only and its
extrapolation to solid product could be questionable. For instance,

C 2014 Institute of Food Technologists®
as the viscosity measurement of meat is not achievable, Zaritzky
and Bevilacqua (1988) used the viscosity of water at the experi-
mental temperature to calculate O2 diffusion in muscle tissues, and
this is definitively not realistic. These authors did not carry out
experimental validation of their calculations. This Wilke–Chang
equation is initially derived from the Stokes–Einstein equation
(Eq. 11), which is also valuable for predicting O2 or CO2 diffu-
sivity, and which relates the diffusivity to viscosity of the medium
and temperature as in Eq. 10
R× T 1
Dp = (11)
NA 6 × π × μ × a
where D is the diffusion coefficient of the migrant (with a radius
of a); T is the absolute temperature, μ is the dynamic viscosity, R
is the gas constant, and NA is Avogadro’s number. This equation,
originally written for fluids and spherical particles undergoing
Brownian motion would remain validated for smaller molecules
(9) such as O2 or CO2 (McCabe and others 2005). The Wilke–Chang
equation (Eq. 10) and the Stokes–Einstein equation (Eq. 11) are
available for O2 diffusion in water, organic liquids, and salt and
glucose solutions (Schumpe and Luehring 1990; Jamnongwong
and others 2010), and also available for CO2 diffusion in liquid
mixtures (water or methanol with various viscosities) (Hikita and
others 1985; Frank and others 1996; Iglauer 2011).
Apart from the Wilke–Chang and the Stokes–Einstein equa-
tions, mathematical models for predicting diffusivity are scarce. In
order to identify if any empirical correlation between food com-
position and diffusivity would exist, we analyzed diffusivity data
from the literature in relationship with the composition of the
food concerned (that is, water, fat content, and protein content).
This exercise was done on CO2 diffusivity only (lack of data on
O2 prevented us from performing a representative analysis) using,
in a first attempt, data taken from the studies on water (Carroll
and others 1991), hake (Simpson and others 2001b), sausage and
(10) ham (Sivertsvik and Jensen 2005), and presented in light color dot
in Figure 8. From this set of data, CO2 diffusivity seems corre-
lated with water and fat content, but not with protein content
contrary to previous studies made on cell tissues (Geers and Gros
Vol. 13, 2014 r Comprehensive Reviews in Food Science and Food Safety 281
O2 and CO2 solubility and diffusivity . . .

2000) or hemoglobin solutions (Gros and Moll 1971), where the ample, material science and engineering where the relationship
authors indicate a decrease in CO2 diffusivity with the increase between the structure of dense matrices and mass transfer proper-
of protein concentration. In order to extend such correlations, ties has already been formalized in some cases).
other data from the literature on fish products (anglerfish, cod,
salmon, tuna, and wolfish in Sivertsvik and others 2004a) were Acknowledgment
added and the result is displayed in dark color dot in Figure 8. This work was supported by the French Ministry of Education
Correlations put in evidence in light color dot in Figure 8 are no and Research (MAP’OPT project).
longer valid when the range of data is enlarged to fish products,
illustrating the difficulty of finding a simple and universal correla- Conflicts of Interest
tion between CO2 diffusivity and food composition. Future work The authors have declared no conflict of interest.
should be carried out in order to deepen predictive models, which
would avoid a time–consuming experimental approach to assess
diffusivity within solid food. Nomenclature
As for solubility measurements, interfering reactions inducing −A: Radius of spherical particle (m)
unwanted and nonmastered O2 /CO2 consumption/production A: Any species of gas (O2 , CO2 , N2 )
could also lead to incorrect assessment of the diffusivity. For AACC International: American Association of Cereal Chemists
instance, in the case of O2 , the occurrence of oxidizable com- International
pounds in the food tends to disturb measurements. O2 consump- AOAC: Association of Official Agricultural
tion within the food product may create a significant delay in Chemists
the establishment of the equilibrium and, consequently, lead to an ATR: Attenuated total reflection
underestimated O2 diffusivity value. In the specific case of CO2 , Ba(OH)2 : Barium dihydroxide
interfering reactions are linked mainly to the enzymatic activity BaCO3 : Barium carbonate
of carbonic anhydrase (EC 4.2.1.1) (Simpson and others 2009). cA : Volume concentration of dissolved gas A
These pH regulatory enzymes catalyze the hydration of CO2 to (kg.m−3 )
bicarbonate (HCO3 – ) and, for example, can contribute to dou- CA : Concentration of dissolved gas A
bling the CO2 transfer in a buffer solution at a pH range of 6.9 to (mol.kg−1 )
7.8 (Geers and Gros 2000). Ca(OH)2 : Calcium dihydroxide
CFU: Colony-forming unit
Conclusion CO2 : Carbon dioxide
In this paper, the different methodologies used to assay O2 and CO3 2− : Carbonate ion
CO2 within solid food products are commented on and discussed D: Diffusion coefficient (m2 .s−1 )
with special emphasis on their implementation in an experimen- FID: Flame ionization detector
tal set–up to assess solubility and diffusivity. Literature data on FTIR: Fourier transform infra-red
O2 /CO2 solubility and diffusivity are listed and discussed. Data H+ : Proton (Hydrogen(1+))
are scarce, especially for O2 solubility and diffusivity due to, mainly, H2 CO3 : Carbonic acid
the difficult implementation of O2 quantification methodologies H2 O: Water
in the experimental set–up of solubility and diffusivity measure- HCl: Hydrochloric acid
ment. Inventory and analysis of this collection have confirmed HCO3 − : Bicarbonate ion (hydrogen carbonate)
some facts: O2 is less soluble in food than CO2 : salt and sugar JA : Gaseous diffusion flux (mol.m.kg−1 .s−1 )
concentrations decrease O2 /CO2 solubility values but obviously k: Kinetic rates of oxidation (L.mol−1 .s−1 )
not the diffusivity values whatever the gas considered. This analysis kHA (T) Henry’s law coefficient for gas A
has also revealed some less known facts such as a lack of repeatabil- (Pa.kg.mol−1 )
ity (that is, for O2 diffusivity in water), some unexpected behavior KOH Potassium hydroxide
as a function of temperature (that is, for O2 and CO2 solubility MAP Modified atmosphere packaging
within oils and also fat products). The role of interfering reactions Mb2+ Myoglobin
(that is, oxidation of fats and proteins, microorganism respiration, MbO2 2+ Metmyoglobin
and so on), on O2/CO2 solubility /diffusivity values (even if it is MgCl2 Magnesium dichloride
well known to influence these parameters) was scarcely quantita- MgSO4 Magnesium sulfate
tively related to the amount O2 /CO2 consumed by the product N2 Nitrogen
during measurement and have usually been uncontrolled during NA Avogadro’s number
solubility and diffusivity measurements. A particular focus of this Na2 SO4 Disodium sulfate
paper is the predictive modeling of solubility/diffusivity as a func- NaCl Sodium chloride
tion of external (mainly temperature) and intrinsic food charac- NaOH Sodium hydroxide
teristics (for example, composition, viscosity, and so on). If some O2 Oxygen
empirical correlations exist to predict the effect of salt and sugar p.v. Peroxide values
concentrations on O2 /CO2 solubility and the effect of viscosity PA Partial pressure of gas A (Pa)
on O2 /CO2 diffusivity, these relations remain validated only for pH Potential hydrogen
aqueous solutions, and extrapolation to real food (for example, pKa Logarithm of the acid dissociation constant
solid product) is questionable. Further work should be conducted ppb Part(s) per billion
in the near future to increase our knowledge on the relationship PSOG Palmitoyl-stearoyl-oleoyl-glycerol
between food structure/composition and O2 /CO2 diffusivity by R Universal gas constant (8.31446
using some approaches taken from other fields of science (for ex- J.K−1 ·mol−1 )

282 Comprehensive Reviews in Food Science and Food Safety r Vol. 13, 2014 
C 2014 Institute of Food Technologists®
O2 and CO2 solubility and diffusivity . . .

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