Applied

Geochemistry
Applied Geochemistry 22 (2007) 249275
www.elsevier.com/locate/apgeochem

Review

Sorption isotherms: A review on physical bases, modeling

and measurement
a,b,* , J.-P. Gaudet b, L. Charlet c, S. Szenknect a,
G. Limousin
`V. Barthes a, M. Krimissa d
a
Atomic Energy Commission, Tracers Technology Laboratory, 38054 Grenoble Cedex, France
b Laboratoire detude des Transferts en Hydrologie et Environnement (CNRS-INPG-IRD-UJF), BP 53, 38041 Grenoble Cedex, France
cLaboratoire de Geophysique Interne et Techtonophysique (CNRS-IRD-LCPC-UJF-Universite de Savoie), BP 53,
38041 Grenoble Cedex, France
dElectricite de France, Division Recherche et Developpement, Laboratoire National dHydraulique et dEnvironnement P78,
6 quai Watier, 78401 Chatou, France

Received 6 January 2006; accepted 7 September 2006

Editorial handling by D. Polya
Available online 21 November 2006

Abstract

The retention (or release) of a liquid compound on a solid controls the mobility of many substances in the environment
and has been quantied in terms of the sorption isotherm. This paper does not review the dierent sorption mechanisms.
It presents the physical bases underlying the denition of a sorption isotherm, dierent empirical or mechanistic models,
and details several experimental methods to acquire a sorption isotherm. For appropriate measurements and interpreta-
tions of isotherm data, this review emphasizes 4 main points: (i) the adsorption (or desorption) isotherm does not provide
automatically any information about the reactions involved in the sorption phenomenon. So, mechanistic interpretations
must be carefully veried. (ii) Among studies, the range of reaction times is extremely wide and this can lead to misinter-
pretations regarding the irreversibility of the reaction: a pseudo-hysteresis of the release compared with the retention is
often observed. The comparison between the mean characteristic time of the reaction and the mean residence time of
the mobile phase in the natural system allows knowing if the studied retention/release phenomenon should be considered
as an instantaneous reversible, almost irreversible phenomenon, or if reaction kinetics must be taken into account. (iii)
When the concentration of the retained substance is low enough, the composition of the bulk solution remains constant
and a single-species isotherm is often sucient, although it remains strongly dependent on the background medium. At
higher concentrations, sorption may be driven by the competition between several species that aect the composition of
the bulk solution. (iv) The measurement method has a great inuence. Particularly, the background ionic medium, the
solid/solution ratio and the use of ow-through or closed reactor are of major importance. The chosen method should
balance easy-to-use features and representativity of the studied natural conditions.
2006 Elsevier Ltd. All rights reserved.

*
Corresponding author. Address: Atomic Energy Commission, Tracers Technology Laboratory, 38054 Grenoble Cedex, France. Fax:
+33 4 38 78 51 34.
E-mail address: guillaumelimousin@yahoo.fr (G. Limousin).

0883-2927/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2006.09.010
250 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275

Contents

0. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
1. Denitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
2. Reaction kinetics and thermodynamic equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
2.1. Relation between thermodynamics and kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
2.2. Kinetic hysteresis and pseudo-irreversibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
Classication and modeling of the isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
3. 3.1. The four main types of isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
3.1.1. The C isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
3.1.2. The L isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
3.1.3. The H isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
3.1.4. The S isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
3.2. Modeling of concave isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
3.2.1. The Freundlich models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
3.2.2. The Langmuir models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
3.3. Generalized modeling of any isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
3.4. Isotherms of uncharged organic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258
3.5. The ion exchange isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
3.6. Surface complexation models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
3.7. How to choose among so many models? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
Experimental methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.1. Inuence of the experimental conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.1.1. The solid/solution ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.1.2. Closed reactor versus open ow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
4. 4.1.3. The composition of the background solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
4.2. Description, advantages, and disadvantages of the methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
4.2.1 The batch method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
4.2.2. The ow-through methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269

5.

0. Introduction eral or organic compounds (trace elements, radio-

Among all phenomena governing the mobility of
substances in aqueous porous media and aquatic
environments, the transfer of substances from a
mobile phase (liquid or gaseous) to a solid phase
is a universal phenomenon. That is the reason why
the isotherm, a curve describing the retention of
a substance on a solid at various concentrations, is
a major tool to describe and predict the mobility
of this substance in the environment. These reten-
tion/release phenomena are sometimes strongly
kinetically controlled, so that time-dependence of
the sorption isotherm must be specied.
This paper is limited to the retention/release of
liquid solutes on natural solid, mineral or organic,
materials. The focus is on the interactions of min-
nuclides, other mineral species such as plant
nutrients, and organic compounds such as trace
organic non-aqueous or soluble contaminants) with
natural mineral or organic materials such as soil,
aquifer or geologic material, and suspended parti-
cles present in porous media, rivers, lakes and
oceans. Many excellent books and papers have
reviewed the literature on these mechanisms (e.g.
Sposito, 1984; Sposito, 1989; McBride, 1994; Bolan
et al., 1999; Pignatello, 2000; Huang et al., 2003), so
that this paper deals with chemical mechanisms only
when it is necessary for understanding their relation
with the isotherm. In contrast, few papers have
reviewed some aspects of isotherms themselves
(e.g. Schweich and Sardin, 1981; Hinz, 2001), which
justies gathering the theoretical and experimental
 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275 251

knowledge on sorption isotherms applied to
geochemistry.
This review provides some denitions, thermody-
namics and kinetics of the reactions involved, then
gives an overview on the empirical and mechanistic
modeling of both sorption isotherms and kinetics of
retention/release, and nally discusses various
experimental methods currently available to mea-
sure sorption isotherms and reaction kinetics.
1. Denitions
release must have been reached, and (ii) all other
physico-chemical parameters are constant. The
word isotherm was specically chosen because
of the inuence of the temperature on sorption reac-
tions; temperature must be kept constant and spec-
ied (e.g. Cornelissen et al., 1997; Werth and
Reinhard, 1997).
Most of the time, the concentration of the com-
pound retained on the solid is calculated by dier-
ence between the initial solute concentration Ca0
and the nal solute concentration C (Fig. 1). In
the case of retention stage, the solid concentration
at equilibrium Q (mol kg1) is given by Eq. (1)

When the retention of a solute on solid particles

is investigated, the remaining solute concentration
of the compound C (mol L1 or kg L1) can be
compared with the concentration of this compound
retained on solid particles Q (mol kg1 or kg kg1),
as shown in Fig. 1. The relationship Q = f(C) is
named the sorption isotherm. The uniqueness of
this relation requires several conditions to be met:
(i) the various reaction equilibria of retention/
V
Q Ca0 C Qa0 1
m
with V being the volume of solution (L), m is the so-
lid mass and Qa0 (mol kg1) is the concentration of
the compound initially retained by the solid, which
must be measured or shown to be negligible. In
the case of a release stage of a compound that is

unequilibrated initial state 1 unequilibrated initial state 2

reactive compound

liquid phase liquid phase

initial concentration: Ca0 initial concentration: Cb0

solid phase solid phase

initial concentration: Qa0 initial concentration: Qb0

retention release
(adsorption) (desorption)

liquid phase
nal concentration: C solid phase:
nal concentration: Q

nal state at equilibrium

Fig. 1. Schematic view of the adsorption and desorption phenomena. This scheme shows that the nal solid concentration Q can be
calculated by dierence between the initial liquid concentration (Ca 0 or Cb0) and the nal liquid concentration C only if the initial solid
concentration (Qa0 or Qb0) is negligible or previously measured.
252 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275

initially present on the solid phase (Fig. 1), the broadest sense (i.e. retention/release) unless other-
quantity of this initially retained compound Qb0 wise indicated.
must be measured previously. The solid concentra-
tion at equilibrium can then be calculated by the
above equation, replacing Ca0 by Cb0 and Qa0 by 2. Reaction kinetics and thermodynamic equilibrium
Qb0 (Fig. 1).
In 1888, this approach to represent solute reten- 2.1. Relation between thermodynamics and kinetics
tion on solids was invented by Van Bemmelen
(1888). This isotherm often cannot of itself provide
A sorption isotherm is often assumed to be con-
information about the type of reaction involved
structed from data obtained at reaction equilibrium.
(Sposito, 1984, p. 122; Veith and Sposito, 1977;
In that case, the adsorption isotherm (made from
Scheidegger and Sparks, 1996). For example, the
measurements of progressive adsorption up to the
retention can be either due to surface retention with-
equilibrium) should be the same as the desorption
out creating three-dimensional structure or to pre-
isotherm (made from measurements of progressive
cipitation of a new solid phase (McBride, 1994, p.
release into the solution up to the equilibrium)
141). Sposito proposed to speak about sorption
because the theory of thermodynamic equilibria
to take into account any type or retention (Sposito,
assumes a complete reversibility of the chemical
1984, p. 122). The precipitation itself is often
reactions and so a unique (C, Q) pair (Strawn and
induced by surface adsorption (the surface acting
Sparks, 1999).
as a template) and thus called surface enhanced
However, sorption mechanisms are driven by
precipitation (Wersin et al., 1994; Ford et al.,
several various kinetically controlled reactions or
2002). This phenomenon was shown by James and
physical phenomena, which have (with redox reac-
Healy (1972) and is of major importance in the for-
tions) the largest variability of reaction times: from
mation of new solid phases in soils and geologic
few seconds to many years (Sparks, 2000). Fig. 2
media (Ford et al., 2002). Due to this diversity of
shows the energetic variations that occur during
retention mechanisms, it could be more appropriate
adsorption or desorption.
to use the term retention isotherm rather than
In Fig. 2 is illustrated the standard free energy of
adsorption isotherm. Some authors even propose
the reaction DG0 (J mol1), which is the dierence
the term curve of disappearance of the solute
between the initial state (free solute compound)
since the retention is often measured by dierence
and the nal equilibrated state (adsorbed com-
between the initial and nal solute concentration
pound). Thus, DG0 is negative since the energy of
(Schweich and Sardin, 1981). It is important to keep
the system decreases during the reaction to reach a
in mind that the retention/release mechanisms are
more stable state. The relation between DG0 and
various and often intricate (Strawn and Sparks,
the reaction constant K (dimensionless) is given by
1999). From now on, the terms sorption,
Eq. (2) (McBride, 1994, p. 14)
adsorption, and desorption will be used in their

DG0
Ke RT
2

molar free energy: G (J mol-1)

activation energy of
adsorption: Ea 1

activation energy of
desorption: Ea -1

standard energy
of the reaction:G 0

reaction pathway: (mol)

Fig. 2. Energetic state of the solid/solute system during a reaction of adsorption or desorption (adapted from McBride, 1994, p. 27).
 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275 253

with R being the gas constant (J mol1 K1) and T Hence, the relation between the reaction energy
the temperature (K). of the reaction and the activation energies (Eq. (4))
In Fig. 2, it is also shown that the thermody-
namic equilibrium is the result of a competition DG0 E1 E1 4
between two contrary mechanisms, represented by
the activation energy of adsorption E1 and desorp- can be directly linked with the relation between the
tion E1. The Arrhenius law (Eq. (3)) provides the thermodynamic constant and the two kinetic con-
relation between the kinetic constants k (dimension- stants (Eq. (5))
less) and the activation energy E (J mol1)
(McBride, 1994, p. 26) k1
K k 1 5

E
By interpreting Fig. 2, it can be concluded that a
k De RT 3 reaction can be thermodynamically spontaneous
(DG0 negative, K > 1), whereas it can be (i) fast,
with D being a dimensionless collision probability either for adsorption or for desorption (low E1
factor.

Fig. 3. Illustration of dierent sorption mechanisms of metal ions (Me) on clay minerals by (a) adsorption by outer sphere surface
complex on exchange sites located on basal planes (hydrated metal) and as inner sphere surface complexes on the edges (dehydrated
metal); or (b) inclusion of the metal into crystal structure by coprecipitation; or (c) precipitation of a new solid phase (after Schlegel et al.,
1999b, 2001).
254 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275

and low E1) or (ii) slow for desorption (high E1)
or even (iii) slow for adsorption and for desorption
(high E1, higher more E1).
2.2. Kinetic hysteresis and pseudo-irreversibility
It is known that several metals and other heavy
elements often show a fast kinetic adsorption reac-
tion by outer-sphere ion exchange followed by slow
adsorptions with specic interactions (Aston and
Duursma, 1973; Amacher et al., 1986; Bangash
et al., 1992; Schlegel et al., 1999b: see Fig. 3). In
the case of slow kinetics for desorption (e.g. Nyeler
et al., 1984; Amacher et al., 1986; McLaren et al.,
Q (Van Bladel and Laudelout, 1967; Ogwada and
desorption isotherm
adsorption isotherm
C
1986, 1998; Bruemmer et al., 1988; Bibak et al.,
1995) or for adsorption, too (e.g. Kuo and Mikkel-
sen, 1980; Padmanabham, 1983; Schultz et al., 1987;
Backes et al., 1995; Lookman et al., 1995; Smith and
Comans, 1996; Schlegel et al., 1999a,b), it is some-
times dicult to know if thermodynamic equilib-
rium is reached (Smith and Comans, 1996; Sparks,
1998). If not, the superimposition between adsorp-
tion and desorption isotherms does not match
(Fig. 4). This mismatch between adsorption and
desorption isotherms is called pseudo-hysteresis
or kinetic hysteresis (Strawn and Sparks, 1999).
A more convenient term could be apparent irre-
versibility (Van Bladel and Laudelout, 1967;
McBride, 1994, p. 91; Ford et al., 2002). The com-
mon term irreversibility can lead to the wrong
conclusion that a part of the solute cannot be des-
orbed at all, whereas it could be a matter of time
Sparks, 1986a,b,c; Comans, 1987; Young et al.,
1987; Verburg and Baveye, 1994). On the other
hand, the saturation capacity of the solid during
adsorption can be underestimated if equilibrium is
not reached (Harter, 1984). The characteristic time
of desorption can be several orders of magnitude
dierent from the characteristic time of adsorption
(Bangash et al., 1992; Ainsworth et al., 1994; Smith
and Comans, 1996). The adsorbed compound can
react, in a second stage, with the solid by (i) slow
diusion inside the solid (e.g. Boyd et al., 1947b;

Fig. 4. Pseudo-hysteresis of the desorption isotherm compared

with the adsorption isotherm when equilibrium is not reached
during the adsorption or desorption stage.

0.010 Sr
inert tracer (tritiated water)

0.008
Sr
concentrati
on (moL-1)
0.006

0.004

[Sr]0 = 0.5 mol L-1

Sr mass balance after 1400 mn: 51%
0.002 mean residence time of the inert tracer: 99 mn

0.000
0 200 400 600 800 1000 1200 1400
Time (mn)

Fig. 5. Breakthrough curve of Sr in an organic soil (from Limousin, 2006). If considering the mass balance only, one could conclude
erroneously to an irreversible adsorption for half of the Sr injected. However, the presence of a thick tail on the Sr breakthrough curve
(while not present for the inert tracer) indicates that desorption is very slow but possibly total.
 256 G.G.Limousin
Limousinetetal.
al./ /Applied
AppliedGeochemistry
Geochemistry22
22(2007)
(2007)249275
249275 255

Bruemmer
a strict asymptotic
et al., 1988;plateau
Fuller(the
et al.,
solid1993;
has a Coughlin
limited 3.log Q log F and
Classication n logmodeling
C of the isotherms 7
and
sorption
Stone,capacity),
1995; Burgos and (ii)et the
al., 1996;
curve Pignatello
does not reach and
Xing,
any plateau
1996; Axe (the and
solid
Anderson,
does not1997; show Pignatello,
clearly a lim- A graph with log C as x-axis versus log Q as y-axis
3.1. The four
provides main
a line types nofand
of slope isotherms
intercepts the y-axis
2000),
ited sorption
or (ii) inner-sphere
capacity). But surface
it often complexation
appears practi-
(see
callyFig.
dicult
3a; e.g.to know
Benjaminif anand
isotherm
Leckie, belongs
1981; Leh-
to atlog F.AccordingtotheFreundlich
mann
the rstandorHarter,
to the 1984;
second Grossl
sub-group.
et al., 1994; Schlegel equation,
Giles et al. the isotherm
(1974) does not
proposed reach amodelling
a general plateau as
et al., 1999b; Manceau et al., 2000), or (iii) crystal- ofC sorption
increases. isotherms, in which 4 particular cases
lization of new solid phases (see Fig. 3b and c; e.g. are now used as the 4 main shapes of isotherm com-
Chrisholm-Brause et al., 1990; Waychunas et al., monly observed (Fig. 6).
3.1.3. The H isotherm
1993; Charlet and Manceau, 1994; Manceau et al., 3.2.1.2. Modied Freundlich model for competitive
This is only a particular case of the L isotherm,
1999; adsorption. It is well known that adsorption is sub-
whereSchlegel
the initial et slope
al., 2001).
is very Thehighduration
(Fig. 6c).of desorp-
This 3.1.1.
tion is was
increased by the time jectedThe C isotherm
to competition between several species (e.g.
case distinguished fromneeded
the others to reverse
because these
the The curve is a line of zero-origin
reactions. This highlights the importance of know- Murali and Aylmore, 1983c; Roy et(Fig.
al., 6a).
1986;It Ban-
compound exhibits sometimes such a high anity means that
ing gash et al.,the ratioInbetween
1992). order to thetakeconcentration
into account of com-
forthe
thehistory
solid that of athe
pollution and taking
initial slope cannotinto be distin- the compound remaining in solution and adsorbed
account petitive phenomena, numerous modied Freundlich
guishedthe fromageing
innity, eect
even if(Strawn
it does and Sparks,
not make sense on the solid is been
the same
1999). models have built,atoften
any concentration.
empirical without Thisany
from aFor the description
thermodynamic andof
point the prediction
view of
(Toth, 1995). ratio is usually named distribution coecient or
dynamic phenomena (diusion through clay materi- physical basis. For example, several modied Fre-
als, advectivedispersive transport through soils and partition coecient:
undlich isotherms (FritzKdand
or KSchundler,
p (L kg1). The
1981;
aquifers, particle transport in natural water . . .), the C isotherm
Sheindorf is often
et al., 1981) used as an easy-to-use
generalize the Freundlich
3.1.4. The Sofisotherm
measurement the mean residence time of water in approximation
equation to m(for a narrow species
competitive range of(Eq.concentration
(8))
the The
systemcurve is sigmoidal
is required and thus
in order has gotita with
to compare point of or very low concentrations such as observed for
inection
the (Fig. 6d). Thistime
mean characteristic type of of the
isotherm
reaction.is always
For trace pollutants) rather than an accurate descrip-
the resultan
example, ofapparent
at least two opposite mechanisms.
irreversible adsorption of tion. But the simplicity of this isotherm must not
!ni 1
aNon-polar organic compounds
long-life radionuclide can often arebeaconsidered
typical case: justify its usemX without verication, otherwise it could
they have irreversible
eectively a low anity in with clays.
aquifers But as the
because soon as
water lead
Qi toF erroneous
iC i ai;jconclusions.
Cj For example, if the8
a clay surface
velocity is high,iswhereas
coveredthe by same
these adsorption
compounds, other
reac- solid has a limitedj1
quantity of adsorption sites, the
organic
tion should molecules are adsorbed
be considered completely morereversible
easily (e.g. for isotherm could be nonlinear because of a possible
aKarimi-Lotfabad
long-term wasteetdisposal. al., 1996; Pignatello,
Such 2000). This
slow desorption saturation plateau.
where ai,j is the dimensionless competition coe-
phenomenon
phenomena canis be
called cooperative
detected by a thick adsorption
tail of the cient of species i in the presence of species j, and
(Hinz, 2001) and
breakthrough curve is during
also observed for surfactants
a ow-through experi- Fi and ni are the coecients of the Freundlich iso-
(e.g. Smith
ment, which et al.,the
is on 1990; Smith not
contrary andpresent
Galan, 1995;
for an Gro- therm of the species i. This formula has been suc-
isman
inert et al.,as2004).
tracer, shownThe presence
in Fig. of a soluble
5 (Limousin, 2006). ligand
cessfully applied to the adsorption of cations
Incan
suchalso provide
a case, a important
it is sigmoidal isotherm
to lower the for back-
metallic 3.1.2. The L isotherm
(Guttierrez and Fuentes, 1991) and anions in soils
species.
ground At low
noise as metal concentrations, the adsorption
far as possible. The ratio between the concentration of the com-
(Roy et al., 1986) and to the adsorption of organic
is limited by the presence of the ligand. The ligand pound remaining in solution and adsorbed on the
compounds on activated organic carbon (Sheindorf
must be saturated and then the adsorption occurs solid decreases when the solute concentration
et al., 1982).
normally (Sposito, 1984, p. 116). The point of inec- increases, providing a concave curve (Fig. 6b). It
tion illustrates the concentration for which the suggests a progressive saturation of the solid. One
adsorption overcomes the complexation. usually makes two sub-groups: (i) the curve reaches
3.2.2. The Langmuir models
3.2.2.1. Simple Langmuir model. Another very com-
mon model is based on reaction hypotheses (Lang-
muir, 1918). The solid is assumed to have a
(a) The C isotherm (b) The L isotherm
limited adsorption capacity Qmax. All the adsorp-
3.2. Modeling of concave isotherms
Q Qtion sites (i) are assumed to be identical, (ii) each site
with strict plateau
retains one molecule of the given compound and
3.2.1. The Freundlich models (iii) all sites are energetically and sterically indepen-
3.2.1.1. Simple Freundlich model. The concave iso- dent of the adsorbed quantity. Then, the following
therm (L or H isotherms) is the most widely reaction is considered:
without strict plateau
met isotherm. The rst model is empirical (Van
Bemmelen, 1888; Freundlich, 1909) and is based C C
on the following relation(c)between the adsorbed
The H isotherm (d) free
The S isotherm
site solute $ surface complex
quantity Q and the remained Q solute concentration Q
C (Eq. (6)) Since activities of adsorbed species are not
clearly
point of dened
inectionthermodynamically, the mass action
law cannot be directly applied to this reaction.
Q FC n 6 Nevertheless, it has been proposed to assume the
with F (L kg1) and n (dimensionless) being two surface activity coecients equal to unity and to
constants (n < 1). This equation is easily linearizable
C calculate the activities Cwith conditional stability
(Eq. (7)) constant, where Q is the solid concentration of
Fig. 6. The four main types of isotherms (after Giles et al., 1974).
 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275
the retained compound on the solid and Qmax Q
is the solid concentration of the free adsorptive site
(Eq. (9))
surface complexQ
L 9
solutefree siteCQmax Q
Therefore, the Langmuir isotherm is (Eq. (10))
LC
Q Qmax 1 LC 10
It can be linearized by (Eq. (11))
Q 13Qi Qmax;i
Qmax L LQ 11
C
A graph with Q as x-axis and Q/C as y-axis pro-
vides a line of slope L and intercepts the y-axis at
QmaxL. According to the initial assumptions, the
isotherm reaches a plateau Qmax (contrary to the
Freundlich isotherm). The constant QmaxL is the ini-
tial slope of the isotherm and QmaxL is often used as
a distribution coecient (Kd) when the concentra-
tions are low enough to justify this approximation.
The constant L corresponds to the anity of the
compound for the solid, while Qmax corresponds to
the adsorption capacity of the solid.
3.2.2.2. Modied Langmuir models for multisite or
competitive adsorption. Although the Langmuir iso-
therm is widely used (Travis and Etnier, 1981), its
linearization sometimes gives poor results: the graph
Q/C versus Q often shows a convex curve. Several
explanations have been suggested. The rst one is
the existence of several types of adsorption sites.
In that case, it is possible to generalize the Langmuir
model to p couples (Li, Qmax,i), each of them corre-
sponding to one type of site (Eq. (12))
pX
Li C
Q Qmax;i 1 Li C 12
i1
This equation can be linearized part by part by using
Eq. (11), providing each couple (Li, Qmax,i). The
adsorption of phosphate on soils was almost per-
fectly described by Eq. (12) with two couples
(L1, Qmax,1) and (L2, Qmax,2) (Holford et al., 1974).
But several authors have demonstrated that the reci-
procity is not true: a perfect adjustment to this model
cannot demonstrate a priori the existence of several
types of sites (Posner and Bowden, 1980; Sposito,
1982) even if other experiments showed that phos-
phate is eectively adsorbed by two types of sites.
The second explanation to the poor linearity of the
function Q/C = f(Q) is the decrease of adsorption en-
257
ergy as the fraction of occupied sites increases. In that
case, the independence between two sites is not valid.
The third explanation proposed is the competition
between two species. Some continuous open-ow
techniques allow ushing the competitive species as
soon as they are displaced, limiting their inuence
(see Section 4.1.2). But it is possible to model an ex-
change between the added species i and the displaced
species j (which remains in competition for adsorp-
tion). Following this hypothesis, the modication of
the Langmuir isotherm yields Eq. (13) (Boyd et al.,
1947a)
Li C i
1 Li C i L j C j
This equation was then generalized (Murali and
Aylmore, 1983a,b,c) for the competition between q
species (Eq. (14))
Li C
Qi Qmax;i 14
1 Pq j1
i
Lj C j
According to this formula, the saturation capacity
Qmax is not aected by competition (the dierent
species being adsorbed by the same adsorptive sites)
and a simple Langmuir isotherm can be used to ob-
tain it. On the contrary, the anity constant Li is
inuenced by the competitive species (Harter and
Baker, 1977). Murali and Aylmore (1983a) used dif-
ferent particular cases to simplify this equation.
However, when the competitive phenomenon is
ion exchange, the ion exchange isotherm approach
should be preferred (see Section 3.5).
3.3. Generalized modeling of any isotherm
In most cases where the concentration of the
studied compound is higher than a trace concentra-
tion, neither the Langmuir nor the Freundlich iso-
therms are consistent with the data and more
complicated models must be applied (Kinniburgh,
1986). Hinz (2001) proposed an equation that could
describe any type of isotherm (Eq. (15))
s ix
X Y Ai;j C pi;j ri;j
Q Qmaxfi15
1 Bi;j C qi;j
j1i1
where Qmax denotes the asymptotic amount of
adsorption at high concentrations, fi is the fraction
of sites of type i (whereas the total number of dier-
ent types of site is x), and si gives the number of
interaction terms between the dierent types of sites.
Ai,j and Bi,j are empirical anity constants and pi,j,
qi,j and ri,j are dimensionless empirical parameters.
258 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275

Although this equation is fully empirical and glnL Qmax dL Lm 18

includes many tting parameters, it has the advan-
tage of decomposing any isotherm into dierent
types of sites.
On the basis of the Langmuir model, another
generalized model for any isotherm was constructed
(Sips, 1948, 1950; Sposito, 1984, p. 120; Nederlof
et al., 1990). The basic idea is to consider any iso-
therm as an integral of Langmuir isotherms
(Fig. 7a). This integral has a density function g(L)
which corresponds to the statistical distribution of
the anity constant L (Eq. (16))
Z 1
LC
QdK16gL
1 LC1
with g being a miscellaneous density function.
Conceptually, each adsorption site provides an
elementary isotherm having its own anity L and
capacity g(L). The complete isotherm is seen as
the sum of all the elementary isotherms, as shown
in Fig. 7a. The function g has been named a
weighting function (Sposito, 1980), a site anity 3.4. Isotherms of uncharged organic compounds
distribution function (Kinniburgh et al., 1983), or
a frequency distribution of the local anity coe-
cient L (Perdue and Lytle, 1983).
By choosing the accurate density function g, any
type of isotherm can be described by Eq. (16) (Sposito, Like many other adsorbed substances, the linear
1984, p. 120; Hinz et al., 1994). In the case of the simpleapproximation of the isotherm is often suitable at
Langmuir isotherm, one can isolate Qmax (Eq. (17))
Z 1
Qmax gL dL17
1
According to Eq. (16), g requires to be a Diracs
function (Eq. (18)) in order for Qmax to be a
constant
with d being the Diracs function and Lm the most
probable L.
The Langmuir isotherm is consequently the sum
of isotherms having the same constant Lm. If the
Freundlich isotherm is needed, g must be a function
whose curve closely resembles a log-normal distri-
bution (not detailed here). Hence, one can concep-
tualize the Freundlich isotherm as the sum of
individual Langmuir isotherms (Fig. 7b) with a
log-normal distribution of their anity constants
(Sposito, 1984, p. 121; Kinniburgh et al., 1983; Hinz
et al., 1994). The same result would be obtained by
assuming that the Freundlich isotherm is a derived
Langmuir isotherm where the adsorption energy
decreases logarithmically as the fraction of occupied
sites Q/Qmax increases (Hasley and Taylor, 1947).
Excellent reviews about the adsorption and
desorption mechanisms of organic compounds have
been written (Pignatello, 2000; Huang et al., 2003).
low concentration (e.g. Schwartzenbach and Wes-
tall, 1981; Groisman et al., 2004), so that a constant
distribution coecient can be applied. Moreover,
non-polar or at least uncharged organic compounds
are hydrophobic and mainly adsorb via Van der
Waals attractions onto the hydrophobic part of solid
organic matter. So, their anity for the solid is often
explained by their anity for solid organic matter
only (e.g. Karickho et al., 1979; Schwartzenbach

(a) isotherm decomposition (general case) (b) decomposition of a Freundlich isotherm

(log-log scale)
Q log Q

Freundlich isotherm
(sum of all the Langmuir isotherms)

complete isotherm
(sum of all the Langmuir isotherms)
slope <1
elementary
elementary
Langmuir
Langmuir
isotherms
isotherms
slopes = 1
C log C

Fig. 7. Conceptual decomposition of an isotherm into several elementary Langmuir isotherms (each of them having a distinct anity and
saturation capacity). The Freundlich isotherm is a particular case where the anity constants are log-normally distributed (after Sposito,
1984, p. 120).
 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275
and Westall, 1981). Although this statement is now
discussed (e.g. Luthy et al., 1997; Sheng et al.,
2001), sorption of uncharged organic compounds
on solid organic matter predominates in most cases,
so that the distribution coecient Kd is proportional
to the mass fraction of organic carbon in the solid foc
(kg kg1) and to the anity constant between the
compound and the organic carbon Koc (L kg1)
(Chiou et al., 1979), as described by Eq. (19)
K d foc K oc
Moreover, Koc is often well correlated to any parti-
tion coecient of the compound between water and
another hydrophobic organic substance (or even its
constant of solubility) by a logarithmic relationship
(Eq. (20)). Most of the time, the chosen coecient is
the easily available octanol/water partition coe-
cient Kow (L kg1)
logK oc a logK ow b 20
with a and b being two constants. This relation was
veried for a wide variety of solids and uncharged
organic compounds (e.g. Karickho, 1981; Schwart-
zenbach and Westall, 1981; Gerstl, 1990), or even
for charged organic compounds for which the
non-polar part of the molecule is big enough.
Although the parameters a and b are obviously
dependent on the nature of the solid organic matter
and on the class of adsorbed organic compound
(Rutherford et al., 1992), these parameters were of-
ten found to remain constant for a wide range of
soils and organic compounds. Thus, it becomes pos-
sible to give an estimation of the adsorption of any
uncharged organic compound at low concentration
on any natural material with two easily measured
parameters: the organic carbon content of the mate-
rial and the octanol/water partition coecient of
the compound.
Regarding the charged organic compounds that
do not behave as described above, as well as regard-
ing the behaviour of uncharged organic compounds
above the limit of linearity of their isotherm, a list of
isotherms of several organic compounds in soils has
been provided (Weber and Miller, 1989).
3.5. The ion exchange isotherms
The mineral species (which are almost all charged
in aqueous solution) are mainly attracted by the sur-
face charges of the solid. Thus, their adsorption is
driven by competing ion exchange phenomena.
When the concentration of the studied ion is low
259
compared to the concentration of other competing
ions, the composition of the bulk solution can be
considered constant and a single-species isotherm
can be applied, although remaining strongly depen-
dent on the composition of the bulk solution. How-
ever, when the concentration of the studied ion
reaches the same order of magnitude as other com-
peting ions, the composition of the bulk solution
can no longer be considered constant and a multi-
species isotherm is needed.
It is possible to take into account the competition
between several ions with modied multi-species
19
isotherms (see Sections 3.2.1.2 and 3.2.2.2). Murali
and Aylmore (1983b) simulated the consequences
of dierent competition features on the shape of
multi-species equilibrium or kinetic Freundlich
and Langmuir isotherms. The ion exchange iso-
therm is another way to describe the competition
between two or more ions when their range of con-
centration is wide. This specic isotherm does not
describe Q versus C, but the molar fraction of
echarges E k of the ion k adsorbed on the solid
((molc kg1)/(molc kg1)) versus the molar fraction
of charges Ek of the ion k remaining in solution
((molc L1)/(molc L1)). The molar fraction of
charges Ek of an ion k is dened by Eq. (21)
Nk
Ek N total 21
with Nk being the normality of ion k (molc L1) and
Ntotal is the total normality (molc L1). The normal-
ity of the ion k is dened as its aqueous concentra-
tion of charges (Eq. (22))
N k mk C k 22
with mk being the valence of ion k (dimensionless),
and the total normality being the sum of normalities
of all present ions or, said dierently, the total con-
centration of charges in solution (Eq. (23))
X
N total Nk23
k
eSo, Ek and E k vary between 0 and 1, according
to
Eq. (21).
It is also assumed that the number of adsorption
sites (surface charges of the solid) is constant, and is
called the intrinsic charge of the solid rint
(molc kg1). For a cation (resp. anion) exchange,
the adsorption capacity depends on the cation
exchange capacity (resp. anion exchange capacity).
But it is important to keep in mind that the cation
or anion exchange capacity is an operational
260 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275
parameter and not an intrinsic property of the solid.
So, it cannot be dened as rint, which is a concep-
tual parameter. The anion or cation exchange
capacity is strongly dependent on the measurement
conditions such as pH or ionic strength (Charlet and
Schlegel, 1999; Limousin and Tessier, 2003). To give
a realistic value to rint, the best method is probably
to measure the anion or cation exchange capacity
with one of the studied ions itself.
The ion exchange isotherm is constructed from
an exchange between two ions i and j, with Ntotal
remaining constant, otherwise the uniqueness of
the isotherm is not valid (e.g. Singhal et al., 1978;
Schweich and Sardin, 1981). Fig. 8 shows NH4/Ca
exchange isotherms on two minerals. In this exam-
ple, the anity of hydroxy-Al interlayered vermicu-
lite is stronger for NH4 because the curve is located
above the non-preference curve (which represents
the equal anity of the solid for NH4 and Ca),
whereas vermiculite does not exhibit signicant
preference for NH4 or Ca. For a homoionic
exchange (two ions with same valence), the non-
preference curve is simply the 1:1 line. However,
the non-preference curve of an exchange between
two ions with dierent valences is not a line because
the purely electrostatic attraction of an ion (without
any specic anity) is proportional to the exponen-
tial of its valence, so that the ion of highest valence
is more adsorbed. Here the exchange between two
Fig. 8. Ion exchange isotherm: exchange between two heterova-
lent ions NH and Ca2+ on vermiculite and hydroxy-aluminum4
interlayered vermiculite, compared with the non-preference curve
of a monovalent/divalent ion exchange. The total normality was
maintained constant at 1 molc L1 (from Evangelou and Lum-
banraja, 2002).
ions i (with valence ai) and j (with valence aj) is
described
aj solid-i ai free j $ ai solid-j aj free i
By similarity with the law of mass action, the selec-
tivity coecient Kex is (Eq. (24))
e a ajsolid-jai
K ex free iaj E j i Ei 24
eisolid-iaj free
Thus,jaa non-preference of the solid means that
i E a j Ea i j
Kex = 1, which leads to the same xed/free ratio
e E k =Ek for both ions only if ai = aj. However, Eq.
(24) is a way to nd a mathematical similarity with
the law of mass action, but it cannot be considered
as a thermodynamic formula: most of the time, ion
exchange deviates from the ideal exchange behav-
iour, so that the selectivity coecient Kex varies sig-
nicantly with Nk (e.g. Singhal et al., 1976). Thus,
Kex values should always be provided with the range
of Nk and ionic strength used for the measurement.
Among many formulas modelling ion exchange, a
simple analytical model was proposed to describe
both ion exchange with possible non-ideal behavior
and inner-sphere complexation (Fletcher and Spos-
ito, 1989).
Sometimes the ion exchange isotherm has a point
of inection. It means that the preferential anity
of the solid for one of the two ions shifts to the other
ion when the fraction of charges occupied by the
rst ion reaches a certain value. It can be caused
by the existence of two types of sites. A well known
example is the K (or NH4)/Ca exchange on the 2:1
Fig. 9. K/Ca exchange isotherm on an Australian soil containing
2:1 clay minerals. The total normality was maintained constant at
0.2 molc L1 (from Bloom and Mansell, 2001).
 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275 261

clays (Fig. 9). For a high fraction of Ca, the ditrigo-
nal sites that are available to ion exchange have a
specic anity for K, and so specically adsorb this
monovalent cation. Then, for a high fraction of K
(when all the available ditrigonal sites are occupied
by K), the other sites do not have specic anity
and the isotherm tends to reach the non-preference
curve of a divalent/monovalent ion exchange (e.g.
Beckett, 1964; Jardine and Sparks, 1984; Bloom
and Mansell, 2001).
3.6. Surface complexation models
Although this paper is not aimed at reviewing
sorption mechanisms, mechanistic models have
been markedly improved during the last 20 years
and are often used to construct sorption isotherms
and to gain mechanistic interpretation of them,
including the inuence of ionic background (e.g.
Sahai and Sverjensky, 1997; Criscenti and Sverjen-
sky, 2002; Sverjensky, 2005). These surface com-
plexation models are based on inner- or outer-
sphere complexations, and can be distinguished
from each other by the way they represent the distri-
bution of the electric potential around the charged
surfaces. The main historical models are: the tri-
ple-layer model (Davis et al., 1978), the constant
capacitance model (Stumm et al., 1980), the Stern
variable surface charge model (Bowden et al.,
1980), the one-pK model (Van Riemsdijk et al.,
1986), the generalized two-layer model (Dzombak
and Morel, 1990), and the charge distribution model
(Hiemstra and Van Riemsdijk, 1996). Good reviews
have been written on the physical bases and experi-
mental applications of surface complexation models
(e.g. Goldberg, 1992, 2004). Thanks to the increas-
ing power of computers, it has become possible to
apply these models to many codes such as these
free-download programs: MinteqA2 (Allison et al.,
1991), PhreeqC (Parkhurst and Appelo, 1999) or
Chess (Van der Lee and De Windt, 1999), which
are continuously improved and appear now to be
essential tools for geochemistry.
3.7. How to choose among so many models?
Table 1 shows the diversity of the formulas that
exist to model sorption isotherms at equilibrium
and Table 2 provides other formulas modelling the
kinetic dependence of adsorption/desorption. These
formulas can be included in solute transfer equa-
tions such as through-diusion or advection-disper-
sion equations (Selim, 1992). The choice of the
adsorption/desorption model can have a great inu-

Table 1
Some classical equilibrium models of adsorption with analytical formulae

Curve shape Model Formula

C curve Linear Q = Kd C
Linear for the species i, in competition with other species Qi PK d C i
n a Cj1 i;j j

L or H curve Freundlich Q = FCn

Freundlich with competition between two species i and j Qi F i C i ai;j C j ni 1
P
Freundlich with competition between m species ni 1
mQi
F iC ij1 ai;j C j
Temkin Q = K1ln(C) + K2
n
RothmundKornfeld (exchange between two ions i and j) QiCiQj K ex C j

QLCQmax 1LC
Langmuir
Langmuir with competition between two species i and j Qi Qmax;i 1LiLi iCi j C jC L
LPiqC iQi Qmax;i
Langmuir with competition between q species
1 LCj1 j j
Q n
Langmuir-Freundlich LC 1LCn
Qmax
Q nLC 1LC
Generalized Langmuir Qmax
Q
RedlichPeterson Qmax LC 1LCn
Q
Toth Qmax LC
11LCn nPx Qsi Ai;j C pi;j ri;j

Hinz Q Qmax i1 fi j1 1Bi;j C qi;j

Q LC 1LC
S curve Sigmoidal Langmuir Qmax
S
C

C: aqueous concentration, Q: solid concentration.

From Murali and Aylmore (1983a,b,c), Selim (1999) and Hinz (2001).
262 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275

Table 2 average of observed concentrations, Cmi is the mod-

Some classical kinetic models of adsorption/desorption with
analytical formulae
el-calculated concentration corresponding to the ith
replication, and wi is a weighting factor (if needed).
Model Formula The model retained must have provided the highest
dQ MSC. This type of quantitative criterion has the
First order h q k 1 Ck 1 Q
dt
dQ
advantage of taking into account the number of t-
h q k C k Q
nth order dt
1 n 1
ted parameters (which should be as low as possible),
dQ
Langmuir kinetic dt h q k 1 CQmax Q k 1 Q as well as a classical least-square calculation.
dQ
Langmuir kinetic with dt
P h q k 1;i C i Qmax n Qj k 1;i
competition Qij1
between n species
Elovich dQ
4. Experimental methods
dt k expPQ
dQ
Power h q kC n Qm
dt
dQ
4.1. Inuence of the experimental conditions
Mass transfer (fraction dt h q kC C im
of immobile water)
First order with partly dQ h q kC C irr
A sorption isotherm does not have any intrinsic
pseudo-irreversible dt
thermodynamic denition: its signicance depends
adsorption
on the conditions from which it is obtained. So,
the measurement method has a strong inuence on
C: aqueous concentration, Q: solid concentration, t: time, h: the results and a brief description of it should
volumetric water content, q: bulk density.
always be provided with the data (Schweich and
From: Murali and Aylmore, 1983a,b,c; Selim, 1999.
Sardin, 1981).

ence on the prediction of solute transfer (e.g. Hinz

4.1.1. The solid/solution ratio
et al., 1994; Brusseau, 1998). An ideal model veries
In many cases, the ratio of solid mass versus solu-
4 properties: it must be eective, comprehensive,
tion volume should theoretically not inuence the
realistic and predictive (Barrow and Bowden,
proportion of adsorbed compound. And most of
1987). Fitting simultaneously all the parameters of
the time, this parameter does not eectively inu-
a model is obviously the worst solution (Westall
ence the shape of the isotherm if it remains in the
and Hohl, 1980; Brusseau, 1998) because many dif-
same order of magnitude. However, numerous
ferent mechanisms could provide the same break-
authors observed a signicant and nonlinear depen-
through curve (see Section 4.2.2). A step-by-step
dence of the solid/solution ratio on the amount of
method must be applied, trying rst to adjust the
adsorption (Aston and Duursma, 1973; OConnor
simplest models (or the most adequate model, based
and Connolly, 1980; Di Toro and Horzempa,
on a mechanistic knowledge of the system) to the
1982; Voice et al., 1983; Di Toro, 1985; Tan and
data and then choosing a more complex model if
Teo, 1987; Boesten and Van der Pas, 1988; Bangash
needed. If a new parameter is introduced into the
et al., 1992; Bajracharya et al., 1996; Porro et al.,
model without any physical justication, its accu-
2000). Despite a few contradictory studies (Koss
racy should be veried by testing its sensitivity in
and Kim, 1990), adsorption is often observed to
dierent conditions and its physical meaning must
decrease with the solid concentration. This phenom-
be concluded carefully. When it is not possible to
enon is called the solid eect. The main reasons
t each parameter separately, it is impossible to give
proposed are (i) the occupied volume of the sus-
any physical meaning to the parameters, and an
pended particles (Celorie et al., 1989) and (ii) their
adequate criterion must be selected to discriminate
aggregation (Voice et al., 1983; Di Toro et al.,
each model. Saiers and Hornberger (1996) proposed
1986) that would prevent an optimal adsorption of
applying an index named model selection crite-
the solutes. For the particular case of clay materials,
rion (Koeppenkastrop and Decarlo, 1993), or
the cationic exclusion volume increases as compac-
MSC (Eq. (25))
tion increases, so that the solid/solution ratio has
!
an additional inuence. The best experimental
Pd
choice is a solid/solution ratio that is representative
2 wi C i C2k
of the natural conditions. In the case of water with
MSC ln Pd i125
suspended particles, the solid concentration is often
2dwi C i Cmi i1
two low to be used in batch. In contrast, the solid/
solution ratio of soils and other geologic media is

where d is the number of data points, k is the num-

ber of tted parameters, Ci is the ith observed con-
centration from the replicate experiments, C is the
 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275
too high to be used in batch (e.g. the solid/solution
of soils is typically 1:1, whereas the solid/solution
ratio of aquifers is closer to 3:1 and the packed clay
barrier materials have a solid/solution ratio higher
than 10:1, up to the limit where only adsorbed water
is present), but can be achieved in column experi-
ments. For batch experiments with these natural
porous media, the range 1 g of solid for 2 mL to
1 g of solid for 4 mL is advised (Porro et al.,
2000). But for strongly adsorbed compounds, this
ideal solid/solution ratio is sometimes too high to
detect the compound remaining in solution. In con-
clusion, the choice of an adequate solid/solution
ratio consists of nding a good intermediate
between experimental constraints and representative
conditions.
4.1.2. Closed reactor versus open ow
The isotherms obtained with ow-through exper-
iments are often consistent with batch data (e.g.
Bond and Phillips, 1990; MacIntyre et al., 1991).
However, the removal (or not) of the solution, i.e.
maintaining (or not) a constant composition of the
solution, can inuence the quantity of adsorbed
compounds. In batch or in re-injected ow methods,
the displaced competitive substances remain in solu-
tion, and thus may interact with the solid. In con-
trast, the open-ow methods supply the system
with a constant solution and the displaced sub-
stances are ushed out and thus do not compete
for adsorption. Therefore, adsorption should be
10.00
1.00
Q (mol g-1)
0.10
0.01
0.01 0.10
C (mol L-1)
Fig. 10. Comparison of two uranyl isotherms obtained by the batch or column method in a silicagoethite medium (after Gabriel et al.,
1998). The authors show that the lower adsorption in batch is due to the competition between uranyl and dissolved silica, while impossible
in column because of continuous ushing.
263
higher for the open-ow methods such as column
or stirred-ow through reactor (Akratanakul
et al., 1983). Some authors have observed this phe-
nomenon (Akratanakul et al., 1983; Miller et al.,
1989b; Porro et al., 2000; Gabriel et al., 1998: see
Fig. 10). But many other studies show that the
adsorption is higher in batch than in open-ow col-
umn (Boekold and Van der Zee, 1992; Grolimund
et al., 1995; Bajracharya et al., 1996). The reasons
for this paradoxical behaviour are mainly (i) the
presence of immobile water in the column, which
acts as a kinetic barrier (Nkedi-Kizza et al., 1985;
Maraqa et al., 1997; Plassard et al., 2000), (ii) the
dierence of solid/solution ratio between batch
and column (OConnor and Connolly, 1980; Voice
et al., 1983; Di Toro, 1985), or (iii) the unachieve-
ment of chemical equilibrium in column if the mean
residence time is signicantly lower than the mean
reaction time (Bilkert and Rao, 1985; Brusseau
et al., 1991; Maraqa et al., 1998; Thomsen et al.,
1999; Altfelder et al., 2001). The spatial chemical
heterogeneities of the medium have also been
invoked (Chrysikopoulos et al., 1990; Brusseau
and Zachara, 1993; Wise, 1993; Fesch et al., 1998),
but they can be neglected compared with the heter-
ogeneity of the pore water velocities (Brusseau and
Zachara, 1993; Johnson et al., 2003). Maraqa
(2001a) investigated the adsorption of an organic
compound on a sandy material in batch, open-ow
column and recirculated-ow column. The distribu-
tion coecients obtained in batch or with recircu-
column
batch
= standard error
1.00 10.00 100.00
264 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275

-4

-5 1

1
log Q (mol
kg-1)-6

ow-through, non-equilibrated water (Martin-Garin et al., 2003)

-7 ow-through, pre-equilibrated water (Martin-Garin et al., 2003)

batch (McBride, 1980)

batch (Davis et al., 1987)

-8 batch (Papadopoulos & Rowell, 1988)

batch (Zachara et al., 1991)

batch (Van der W eijden, 1995)
-9
-10 -9 -8 -7 -6 -5 -4 -3
-1
log C (mol L )

Fig. 11. Eect of the background composition of the solution on the adsorption isotherm of Cd onto calcite. This eect was either tested in
batch (with dierent background compositions) or in stirred ow-through reactor with pre-equilibrated or unequilibrated water. Each
concentration of the isotherms constructed from stirred-ow through experiments corresponds to one complete breakthrough with the
same injected concentration. The solid concentration is given in mol m 2 to take into account the dierences in specic surface area of the
samples (after Martin-Garin et al., 2003). See above-mentioned references for further information.

lated-ow column are similar whereas they are 30
170% higher in open-ow column. Therefore, the
dierences usually observed between batch and
ow-through methods could not be due to the dier-
ent solid/solution ratios but only to the removal of
the solution. Since many systems of interest are
open and dynamic in nature (solute diusion in
clays, solute transfers in soils and aquifers, particle
transport in lakes or rivers. . .), one can think that
open-ow methods are closer to these natural condi-
tions and thus should be preferred as often as possi-
ble (Schweich et al., 1983; Sparks, 1985), taking into
account the background composition of the injected
solution.
the adsorption of Cd on calcite in stirred-ow
through experiments (Fig. 11) and managed to
describe the observed dierences among their results
and other batch data by modelling the eects of pH
and Ca concentration.
4.2. Description, advantages, and disadvantages of
the methods
Table 3 summarizes the main characteristics,
advantages and disadvantages of each method for
an appropriate purpose.

4.2.1. The batch method

4.1.3. The composition of the background solution
As indicated in Section 3.5, the ionic and molec-
ular background of the solution is of major impor-
tance, especially when adsorption or desorption is
governed by competing mechanisms such as ion
exchange. If the solution is well equilibrated with
the solid, the dierences between experiments per-
formed with deionised or pre-equilibrated water
can be negligible. This condition can be completed
for batch experiments with a solid/solution ratio
high enough. However, for any other condition
(batch experiment with low solid/solution ratio or
ow-through experiment), the background compo-
sition of the solution must be as close as possible
to what is expected or measured in natural condi-
tions. For example, Martin-Garin et al. (2003),
showed the inuence of the pre-equilibration on
The batch is far easier to use than any other
method. The solid is shaken in the solution until
the adsorption or desorption equilibrium is reached.
Then, the remaining solute concentration is
measured.
The disadvantages are numerous. The solid/solu-
tion ratio is often either too high compared with the
natural conditions in rivers, lakes or seas, or too low
compared with the natural conditions of porous
media. Moreover, the hydrodynamic conditions of
natural porous media are not met. A long term
experiment with continuous shaking can lead to side
reactions (Sposito, 1984, p. 113) such as the destruc-
tion of particles, which prevents the study of very
slow reactions. As a consequence, the batch method
is very useful as a preliminary experiment but
extrapolation to porous media requires other
investigations.
 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275 265

Table 3
Main characteristics of experimental methods for the measurement of adsorption/desorption isotherms and kinetics

Method Solid/ Adsorption Desorption Inert Main advantage/Main Appropriate purpose

solution measurement measurement tracer disadvantage
ratio

Batch Chosen Easy Dicult (step No Easy-to-use/unrealistic for Preliminary

(<1 kg L1) by step) porous media measurements
Chosen Easy Flow-through with chosen solid/ Reaction kinetics, release
Stirred ow Easy Possibly
(<1 kg L1) solution ratio measurement
cell no
High Solid/solution ratio of porous Transfer in poorly
Repacked Yes
(Pbulk Easy Easy media/structure destroyed structured porous media
column
density)
High
(Pbulk
Zero- density) Dicult (or Easy Possibly Negligible dispersion/low Kinetics of release
length fast reaction) no reaction time
column

4.2.2. The ow-through methods ments must be performed in dierent conditions

A solution that does not contain the considered
reactive solute is continuously injected at the inlet
of the reactor. Then, the reactive compound is (i)
instantaneously injected at the inlet of the reactor
(Dirac injection) or (ii) continuously injected during
a time period (nite step injection) or (iii) continu-
ously injected after a given time (innite step injec-
tion). The outlet solution can be ushed or re-
injected (Maraqa, 2001a). In addition, one can
adjust the ow rate, so that the mean residence time
can be chosen to be higher or close to the mean
reaction time, or even lower if the reaction is not
instantaneous. Thus, the kinetic dependence is eas-
ier to investigate than in the batch method.
An excellent review has been written about the
relations between sorption isotherms and break-
through curves (Schweich and Sardin, 1981) and
some of the simple rules were formally established
by Golden (1969). A recent review provides some
other examples of relations between isotherms and
breakthrough curves (Seidel-Morgenstern, 2004).
In the common case of a concave isotherm, the
asymmetry of the breakthrough curve is strength-
ened. However, it is important to remember that
many other mechanisms can create asymmetry, such
as (i) the presence of immobile water (e.g. Van
Genuchten and Wieranga, 1976, 1977; Van Genuch-
ten et al., 1977; Valocchi, 1985; Ma and Selim, 1997;
Maraqa, 2001b), or (ii) slow adsorption or desorp-
tion kinetics (e.g. Rubin, 1983, or see Fig. 5), or
(iii) preferential owpaths (Jury and Roth, 1990;
Jury and Fluhler, 1992), or (iv) colloidal transport
(Ryan and Elimelech, 1996; Kretzschmar et al.,
1999), or (v) simply a low ratio between advection
and dispersion (low Peclet number). So, the experi-
(injected concentrations, ow rates, etc.) in order
to test their inuence independently and to avoid
erroneous conclusions. In the presence of noticeable
asymmetry, the main experimental diculty consists
in measuring precisely the tail (Schweich and Sar-
din, 1981; Altfelder et al., 2001; Maraqa, 2001a;
Pang et al., 2003). Most of the time, the recovery
of the adsorption or desorption isotherm from a
breakthrough curve needs to solve a system contain-
ing the transport equation of the inert tracer added
to an equilibrium and/or a kinetic model of the
adsorption/desorption. This mathematical issue is
often complex. However, one can provide two sim-
ple qualitative rules: (i) if two adimensioned break-
through curves of a reactive tracer made with two
dierent injected concentrations and the same ow
rate are not superimposed, it means that the iso-
therm is not linear; and (ii) if two adimensioned
breakthrough curves of a reactive tracer made with
two dierent ow rates and the same injected con-
centration are not superimposed, it means that a
kinetic eect is involved. More details about the
recovery of an isotherm from a column or a stir-
red-ow breakthrough curve are discussed in the
following paragraphs.
4.2.2.1. The stirred ow-through reactor. This system
is also named stirred ow cell or stirred ow
chamber and was developed following the concept
of the continuous-ow stirred tank (Carski and
Sparks, 1985; Rimstidt and Dove, 1986; Randle
and Hartmann, 1987; Miller et al., 1989a; Schnabel
and Fitting, 1989; Seyfried et al., 1989; Sparks,
1989; Zhang and Sparks, 1993) that is widely used
in engineering and industry. It consists in injecting
266 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275

a step of the reactive tracer through a stirred cell
containing a known mass of the solid in contact
with the solution, and then comparing the break-
through curves of the reactive solute with that of
an inert tracer.
For a perfect stirred ow-through reactor, the
solution composition is assumed to be homoge-
neous within the reactor and equals the outlet one.
The breakthrough curve of an inert tracer following
a step injection from C = 0 to C0 (Fig. 12b) is given
by Eq. (26) (Denbigh, 1944; Villermaux, 1993)
u
C C 0 1 expt t0 26
V0
where t is time, t0 is the instant when the tracer is
injected, / (L s1) represents the ow rate and V0
(L) is the volume of the solution inside the reactor
(i.e. the volume of the reactor minus the volume
of the solid). The ratio V0// denes the mean resi-
dence time in the reactor for an inert tracer. For
the desorption stage (switching back the injected
concentration to zero), the breakthrough curve of
an inert tracer (Fig. 12b) is given by Eq. (27) (Den-
bigh, 1944; Villermaux, 1993)
u
C C 0 expt t1 27
V0
where t1 is the instant when the injection of the tra-
cer is stopped.
Knowing these two equations, it is often not nec-
essary to measure the breakthrough curve of an
inert tracer: most of the time, there is no dierence

(a) Batch
stage 1: fast adsorption

0.4
stage 2: equilibrium or slow adsorption

gstage 3: adsorption enhanced

0.3 by particle disrupting ?

C /C0
C0 = 10-4 mol L-1

0.2
maximum
median
minimum
0.1
0 1 10 100 1000
Time (h)

(b) Stirred ow-through reactor

1.0 C0 = 10-4 mol L-1

inert tracer
0.8
cobalt, mean water residence time = 1 h
cobalt, mean water residence time = 20 h
0.6
C /C 0

0.4

0.2

0.0
0 2 4 6 8 10 12 14 16 18 20 22 24 26

adsorption stage desorption stage

V/V0

Fig. 12. Adsorption kinetics of Co on a soil measured (a) in batch and (b) in stirred ow-through reactor with the same background
solution (from Limousin, 2006). The batch method indicated a fast adsorption, but it prevented from concluding to a slow reaction
because of long-term side eects, such as particle disrupting. On the contrary, the stirred-ow through method used with two dierent
mean water residence times conrmed the existence of slow reactions.
 268 G.G.Limousin
Limousinetetal.
al./ /Applied
AppliedGeochemistry
Geochemistry22
22(2007)
(2007)249275
249275 267

between
studied concentration
the computed range and measured
(from C =breakthrough
0 to C0) into dependence).
1995; Martin-Garin
The dierence
et al., 2003;
between
Szenknect
the surface
et al.,
curve
n concentration
when the solidintervals
is well(the
mixed.
ith interval
For a reactive
being from area
2005),of the
andadsorption
provides satisfactory
stage and the results
surface
to predict
area
solute,
C = 0 totheCibreakthrough
). Then, the corresponding
curve deviates adsorbed
from that ofthe
thebreakthrough
desorption stage
curves provides
obtained thewith
amount
a repacked
of reac-
predicted
fraction between
in Eq. (26) C=(resp.
0 and (27))
Ci isand
calculated
the amountusing tive
column
solute(Szenknect
which wasetpseudo-irreversibly
al., 2005). Moreover, adsorbed
the ow
ofthe
adsorbed
surface (resp.
area between
desorbed) thesolute
breakthrough
is given by curves
the (since
rate (and
the quantity
thus the ofmean
adsorbed
contact solute
timecan
of the
be solute
negli-
surface
of the inert
area and
separating
reactivethe
tracers
breakthrough
inside this curve
interval
of gible
with compared
the solid) can
withbethe adjusted
total injected
to measure
quantity,
the inu-
this
the
(Fig.reactive
13). Each
solute
of these
and ofcalculations
the inert tracer
provides
(Fig. one
13). type
enceofofmass
chemical
balance
kinetics
is often
(e.g.
more
Bar-Tal
appropriate
et al., 1990;
to
Modelling
point (Ci, the
Qi) of
breakthrough
the isotherm. curve
Thisofmethod
a reactive
has sol-
the know
Eick ettheal.,
amount
1990; of
Nagy
pseudo-irreversibly
and Lasaga, 1992; adsorbed
Van Cap-
ute
advantage
consists of
in avoiding
solving aanysystem
model of several
assumption equations:
and compound
pellen andthan Qiu, the
1997a,b;
dierenceMartin-Garin
betweenet theal.,
total
2003),
Eq.
requiring
(26) oronly
(27) one
coupled
breakthrough
with an equilibrium
curve to construct
or a injected
as shown mass
in Fig.
and13 the
(Limousin,
total recovered
2006). mass). With-
kinetic
a complete
modelisotherm.
(e.g. Bar-Tal
However,
et al., 1990
several forissues
some out coupling the chemical-transport model, it is pos-
analytical
remain. First,
solutions
a precise
taking
isotherm
into account
requiresa kinetic
a high sible to construct the isotherm by discretizing the
number of points. But the greater the concentration
intervals are, the smaller is the precision on each 4.2.2.2. The repacked column. This column is packed
surface area between the breakthrough curves of with the solid particles, and the solution goes
the inert and reactive tracers. In addition, the through. An example of typical breakthrough
greater the non-linearity of the isotherm, the smaller curves of inert and reactive tracers is shown in
the dierence between two intervals must be in Fig. 5 (Limousin, 2006). Like the stirred ow-
order to have good precision, which leads to the through reactor, this method has the advantage of
strong assumption that the reaction must be consid- being an open-ow method. So, the chemical kinet-
ered instantaneous not only compared to the mean ics and the release stage can be studied more easily
residence time of the inert tracer, but also to the than with the batch method (Sparks et al., 1980;
time corresponding to each concentration interval. Sparks and Rechcigl, 1982). Moreover, the solid/
These limits in the precision of this method explain solution ratio is representative of natural porous
why the coupling-transport models are often pre- media. Furthermore, the experiments can be run
ferred. Martin-Garin et al. (2003) showed, however, either in water saturated or unsaturated conditions
the feasibility of constructing the isotherm by per- (Plassard et al., 2000; Porro et al., 2000). However
forming several breakthrough experiments with dif- this ow-through method has some disadvantages.
ferent concentrations, each of them providing only For example, the duration of the experiment can
one point of the isotherm by the total mass balance be long, especially for strongly adsorbed solutes or
between the reactive and the inert tracer, instead of in the case of compacted of unsaturated clay mate-
several points for one breakthrough curve. This rials with low hydraulic conductivity.
method is valid only if the isotherm can be consid- The main disadvantage of this technique is that
ered linear in the concentration range of each break- the system is not perfectly mixed and the break-
through curve, but it provided good consistency through curve of the reactive compound also con-
with other batch data (Fig. 11). tains the hydrodynamic dispersion of the medium.
The two main disadvantages often pointed out in So, a comparison with an inert tracer is unavoidable
the literature are (i) sealing, which prevents con- to know how chemical reactions are involved.
ducting long experiments and (ii) the magnetic stir Taking into account hydrodynamic processes adds
bar placed inside the cell that progressively destroys to the complexity of the problem and, contrary to
the solid particles (Deitsch and Smith, 1995; Pigna- the stirred-ow through method, it prevents con-
tello, 2000). These two problems can be avoided (i) structing the isotherm without choosing a chemical
by reversing the sense of the ow inside the cell model. Some analytical solutions for the case of
intermittently without reversing the complete circuit negligible dispersion (De Vault, 1943; Glueckauf,
`(Heyse et al., 1997; Barthes et al., 1945) have shown their limitations because of
2004) to prevent the dispersion or of the presence of immobile
the lters from being sealed, and (ii) by using an water (Glueckauf and Coates, 1947; Merriam and
external system that shakes the cell instead of plac- Thomas, 1956). Thus, tting a coupling chemical-
ing a stir bar inside (Furrer et al., 1993; Zysset and transport model to the breakthrough curve and then
Schindler, 1996). verifying the parameters of the model in dierent
In conclusion, the stirred ow-through reactor is conditions remains the simplest method to obtain
much more appropriate than the batch method to information on the adsorption or desorption
study the release stage (e.g. Grolimund et al., isotherm. Moreover, several numerical models have
been developed to calculate the adsorption or

Fig. 13. Construction of the adsorption isotherm from the breakthrough curve of an inert and a reactive tracer obtained with the stirred
ow-through reactor, assuming that the reaction is instantaneous. The relation Rbetween the hatched surface area A i of the breakthrough
R ttttow rateow ratecurve and the solid concentration Qi is given by: Qi solid
mass Ai solid mass t0i C inert tracer dt t0i C reactive compound dt. The desorption
isotherm is obtained by the same procedure with the desorption stage of the breakthrough curve.
 G. Limousin et al. / Applied Geochemistry 22 (2007) 249275
desorption isotherm from dispersive breakthrough
curves (e.g. Schweich et al., 1983; Kool et al.,
1989; Grioen et al., 1992).
4.2.2.3. The zero-length column. An original method
has been proposed to nullify the eects of the por-
ous network (hydrodynamic dispersion, preferential
pathways, immobile water, etc.). The column is thin
enough so that its dispersivity is close to zero and
the breakthrough curve is only sensitive to the
chemical properties of the medium (Eic and Ruth-
ven, 1988; Ruthven and Eic, 1988).
This method is particularly suited to highly
adsorbed compounds or to desorption studies
(especially for already polluted porous media).
Compared with classical column methods, this
technique can be performed without an inert tra-
cer. However, the length of the column must be
thin enough and the ow rate must be high enough
to overcome the dispersive eects. Thus, this
method is often not suitable for adsorption
measurements.
5. Conclusion
The sorption isotherm is a common approach to
describe a great diversity of retention/release phe-
nomena. This is very useful and often unavoidable
to understand and predict the mobility of sorbing
substances in the environment. However, this
approach is macroscopic and empirical in nature,
thus not saying, by itself, anything on the compli-
cated mechanisms involved. In particular, it is
important to verify if thermodynamic equilibrium
is reached within the reaction- (or residence-) time,
both for the retention and for the release stage of
the compound. Otherwise kinetic experiments must
be considered.
Since the isotherm is not an intrinsic property of
the substance/solid couple, the measurement
method has a great inuence on the results. Thus,
it must be chosen carefully and always described
with the results in detail.
Other methods allow the investigation of the
retention microscopically, particularly with spectro-
scopic and microscopic tools. They have provided a
new ecient way to verify several assumptions used
in isotherm interpretations on the solid structure
and retention/release mechanisms, thus leading to
more condence in structure-based and mecha-
nism-based complexation models. These models
should replace the traditional Kd approach. On
269
the other hand, the increasing power of computers
makes possible not only improving mechanistic
models of speciation, but also running Molecular
Dynamic Experiments. However, natural media
are such complicated mixtures of numerous mineral
and organic compounds that empirical approaches
such as the sorption isotherm will be still used
for a long time.
Acknowledgements
The authors acknowledge partial funding from
Electricite de France and French Atomic Energy
Commission. We thank all the reviewers who partic-
ipated in the improvement of this paper.
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