60 Ecological Processes | Adsorption
Adsorption
Y Artioli, University of Padua, Padua, Italy
ª 2008 Elsevier B.V. All rights reserved.
Introduction
The Chemistry of Adsorption
Equations for Adsorption
Introduction
Adsorption is the process when a molecule, or ion, called
adsorbate present in a gaseous or liquid bulk sticks on the
surface of a solid, rarely a liquid, called adsorbent. It is a
surface process, that is, only the surface of the adsorbent is
involved, and adsorbate does not diffuse into the structure
of the adsorbent (in this case indeed the process is called
absorption). The reverse process, that is, the drop of a
molecule from a solid surface, is called desorption.
This process occurs naturally in the environment; it
has also many industrial applications (e.g., to fractionate
air mixture or to depurate gas or liquid emissions). It can
trigger other important processes such as enzymatic reac-
tions or ion exchange.
The Chemistry of Adsorption
It is possible to define two kinds of adsorption: physical
adsorption (or physisorption) when the adsorbate adheres
to the surface because of physical forces, and chemical
adsorption (or chemisorption) if the adsorbate is chemi-
cally bound to the adsorbent’s surface.
Physisorption occurs thanks to van der Waals interac-
tions: these are attractive forces due to weak electrostatic
interactions occurring between molecules. If the adsor-
bate molecules hit the surface with low energy, this can be
dissipated as heat by vibration of the lattice of solid;
hence, they can be trapped on the surface. If the mole-
cules hit the surface with too much energy, this cannot be
dissipated by the adsorbent, and they bounce away.
The change of enthalpy is so low, typically less than
20 kJ mol1, that both, adsorbate and adsorbent, do not
undergo any change in their chemical status: no new
bounds are formed and no change in the energetic state
is observed, a part of a low heating of the adsorbent.
Indeed, the physical bound is highly labile, and the pro-
cess can easily revert even simply as a consequence of
vibrational motion. It has been estimated that at typical
environmental temperature (about 20  C), lifetime for
physisorption is about 108 s, and only with very low
Adsorption in Ecology
Further Reading
temperature (about 170  C) lifetime is of the order of
seconds. For this reason, physisorption is a relevant pro-
cess only at low temperature, always under the critical
temperature of the adsorbate. Given the nature of the
forces that cause physisorption, this is a process that can
occur in multilayer: as long as the adsorbed molecules are
not able to completely shade the electrostatic potential,
new adsorbate can adhere to the adsorbent’s surface, even
if already covered by other molecules. Of course, the
enthalpy required to desorb these new molecules is
lower; then the strength of adsorption (and its lifetime)
decreases with the increasing of the number of layers of
adsorbate already stuck to the surface.
Contrary to physisorption, chemisorption involves
stronger forces: indeed in this case adsorbate forms a
real chemical bond (usually covalent) with the adsorbent’s
surface. The change in enthalpy is greater (from 40 to
400 kJ mol1, always negative as adsorption is a sponta-
neous process). Chemisorption can be an activated
process, that is, it requires that the adsorbate has a mini-
mum of energy in order to be sorbed. This depends on the
presence of an energetic barrier between the physisorbed
and chemisorbed state (Figure 1): if this barrier is higher
than the energy of the free molecules, then the adsorbate
will chemically bond to the adsorbent only if it has more
energy than the barrier, otherwise it will be desorbed. In
case the barrier is lower than the energy of free molecules,
all the molecules physisorbed can quickly form a chemi-
cal bond with the adsorbent surface and chemisorption
will occur rapidly.
Due to higher enthalpy involved, vibrational motions
are not able to break the covalent bonds; hence, lifetime at
environmental temperature (20  C) is of the order of
thousands of seconds (i.e., 1 h), and only at high tempera-
ture (100  C) it decreases to 1 s.
Desorption from chemisorbed state is then always an
activated process: indeed, to detach from the surface,
molecules need to be supplied with energy to break the
bonds. Only a monolayer of adsorbate can be chemisorbed
to adsorbent surface: once if the whole surface is covered
by adsorbate’s molecules, so that no more sites are avail-
able to the bond, then adsorption ends, or yet better, it is
at dynamic equilibrium with desorption.
 Ecological Processes | Adsorption 61

Potential energy
Potential energy

Ea,c
ΔHp
ΔHp
d d
ΔHc
ΔHc

Figure 1 Diagram of energy of adsorption depending on distance (d) of adsorbate molecule from surface. Solid line is for
physisorption, involving low enthalpy (
Hp), dashed for chemisorption, where the energy required is higher (
Hc). On the left is the case
of activated chemisorption: Ea,c is the activation energy for chemisorption.

Chemisorption is prepatory to other two important concentration if it dissolved in a solution). In case of

processes: heterogeneous catalysis and ion exchange. dissolved adsorbate,
Both processes, indeed, need that the substances involved
are strictly bound in order to start and complete: catalysts q ¼ f ðC Þ
require that substrate is strictly bound on their surface in
order to foster the reaction, and the same is true for ion
where q (mg g1) is the mass adsorbed per mass unit of
exchanger, which requires a chemical bond with the
adsorbent and C (mg l1) the concentration of adsorbate
solute to exchange the ion.
in the environment. Such relationships are called iso-
As any other chemical reaction, adsorption is influ-
therms, which means that their validity is limited to the
enced by the physical and chemical conditions of the
case of constant temperature.
environment, and in particular by temperature, pH, and
There are several kinds of isotherms. The most used
redox conditions. Being a surface process, a key factor for
are the isotherm of Langmuir and the isotherm of
adsorption is the surface of the adsorbent: obviously
Freundlich.
adsorbent with more surface has more capacity to adsorb
The Langmuir isotherm is described by the following
substances. For this reason, the best adsorbents are porous
equation:
substances, or more generally the ones with the greater
surface per unit volume (e.g., activated carbon and clay).
bqm C
q¼
1 þ bC

Equations for Adsorption
As discussed in the previous section, adsorption usually
involves low enthalpy and has a short lifetime. This
means that adsorption and desorption have low activation
energy, and then the amount of molecules adsorbed/
desorbed from the adsorbent is very high: equilibrium is
reached fast, if physicochemical environmental condi-
tions do not change.
Hence, adsorption is usually described through a rela-
tionship independent from time between the amount of
adsorbate attached to the adsorbent and the amount in the
environment (expressed as a pressure if it is a gas, a
where qm (mg g1) is the maximum amount of adsorbate
in the adsorbent and b (l mg1) is the equilibrium constant
related to the enthalpy of the process. It can be easily
derived considering that at equilibrium the amounts (per
unit time) of molecules adsorbed and desorbed are equal,
that is, the rates of both reactions are the same.
Four hypotheses are behind this formulation. First
adsorbate cannot attach indifferently on the surface, but
only on particular sites that satisfy appropriate conditions,
that is, they are able to establish a link with the adsorbate
(by way of van der Waals forces or chemical bonds).
Second, adsorption occurs only in a monolayer, that is,
once a site is occupied by a molecule, it cannot bind to
62 Ecological Processes | Adsorption
another one: this leads to the saturation shape of the
isotherm. Third, sites are energetically equivalent, that
is, the energy involved is the same in all sites. Fourth, the
molecules adsorbed are not able to influence adsorption
(and desorption) because they do not interact with the
other molecules of adsorbate. The last two assumptions
can be summarized stating that adsorption occurs homo-
geneously (even if discreetly) on the surface.
Langmuir isotherm is shown in Figure 2. The shape of
the curve clearly depends on parameters; however,
usually the saturation is reached quite fast.
The equation for the Freundlich isotherm is
q ¼ aC 1=n
where a (mg g1) is the mass adsorbed with a unitary
concentration and n is an empirical constant usually
greater than 1. As for Langmuir, Freundlich model is
not empirical but it is theoretically based. Among all the
assumptions behind this model, it is important to mention
two of them.
First, adsorption is no more monolayer, but several
layers of adsorbate can be attached on the adsorbent.
The mathematical formulation does not even provide
for an asymptote: adsorbent would never saturate and
would continuously bind to adsorbate. This is obviously
not true in nature, and in fact Freundlich isotherm is not
able to fit experimental data when concentration of adsor-
bate is high.
The second important assumption is that the energy
required for adsorption is not constant, but it varies and it
is exponentially distributed. The strength of bonds is not
homogeneous due either to the physicochemical charac-
teristics of sites or to the number of molecules already
adsorbed. In particular, more the number of molecules
bound to a site, less probable is that another molecule
binds to the same site because an (exponentially) higher
energy is required.
q,θ
Langmuir Freundlich BET
C,z
Figure 2 Isotherms of Langmuir (solid line), Freundlich
(dashed), and BET (dotted). They describe the amount of
adsorbate expressed in term of mass fraction q (or fraction of
sites occupied  for BET) depending on its concentration C (or on
pressure of gaseous adsorbate relative to saturation pressure).
This is well clear also by looking at the Freundlich
curve (Figure 2): the slope decreases when concentration
of adsorbate increases.
The parameter values for both isotherms are usually
estimated by interpolation of empirical observation.
Parameters change in response to a variation of tempera-
ture, leading to a decrease of the fraction adsorbed when
temperature rises, and vice versa. In fact, higher tempera-
ture means stronger vibrational motion, that is, a higher
probability for adsorbate to break weak van der Waals
bonds. The slope of both curves decreases, and Langmuir
curve reaches the asymptote for higher concentration of
adsorbate.
Always from empirical observation, it appears that
Freundlich’s model is usually more appropriate to
describe adsorption from liquid solutions, whereas the
Langmuir’s one tends to fit better the data on adsorption
of gases.
Another isotherm that fits well the data of adsorption
of gases on solids is the BET isotherm (after Brunauer,
Emmet, and Teller). The main assumption of this model
is that the first layer of adsorbate can adsorb on its another
layer, and this adsorption is also regulated by a Langmuir
equation:
cz
¼
ð1 – zÞf1 – ð1 – c Þzg
where  is the fraction of sites on the adsorbent that have
adsorbed a molecule, z is the ratio between the pressure of
adsorbate and its saturation pressure at the same tempera-
ture, and c is a constant that depends on enthalpy of
desorption and vaporization.
As in the Freundlich’s model, BET isotherm implies an
endless adsorption, even if in this case the slope of the
curve increases with the pressure of adsorbate (Figure 2).
There are several other isotherms, sometimes specific
for some adsorbate–adsorbent couples, for instance, the
Redlich–Peterson, the Sips, and the Temkin isotherms.
A simpler approach is to assume that adsorption is
linearly dependent on the concentration of adsorbate:
q ¼ kC
where k is the partition coefficient. This simple relation-
ship has clearly a strong limitation, given that q increases
very fast with concentration. However, for diluted adsor-
bate, this model can easily be used with small or no error:
indeed, it is an approximation of the Langmuir model in
conditions far from saturation. The value of the partition
coefficient can be estimated via empirical observation, or,
for nonionic compounds like organic chemicals, can be
estimated through
k ¼ foc koc
 Ecological Processes | Adsorption 63

where foc is the fraction of carbon in the adsorbent and koc
is the partition coefficient of adsorbate in the organic
carbon. The latter can be estimated directly from the
well-known kow (partition coefficient of a substance in
an octanol–water mixture).
Due to the particular affinity of organic chemicals and
organic carbon, it is assumed that adsorption occurs only
on the carbonic fraction (i.e., sites are located only on this
fraction).
Even if adsorption is usually a process at the equili-
brium, sometimes it is also important to study its
dynamics, for instance, in those systems where the contact
between adsorbate and adsorbent is too small (e.g., rains
percolating through an arid soil). The assumption and
methodology to derive the dynamic law for adsorption
are similar to the theory of the two films used for absorp-
tion: the single film considered to separate the bulk of
solution where adsorbate is uniformly diluted due to eddy
diffusion, and the film near the surface of adsorbent,
where only molecular diffusion occurs (Figure 3).
In this case the second film is not necessary because
adsorption is a surface process; molecules stick to the
surface and do not enter the solid structure.
Nonetheless, there are two resistances that contrast the
motion of adsorbate: the first is the resistance due to
stagnant film (i.e., molecular diffusion, proportional to
the ratio between the molecular diffusivity DAB and the
thickness  of the film); the other is the resistance due to
motion into the pores of solid. In order to complete
Liquid bulk
Liquid film
adsorption till the equilibrium, molecules need to move
through tortuous pores to reach all the sites available.
Mass transfer in the fluid film is described by
qC
¼ kf ðC – Ci Þ
qt
where kf is the mass-transfer coefficient in the fluid film, 
is the ratio between area and volume of adsorbent, and Ci
the concentration at the interface. This is the same equa-
tion as used in absorption case, except for  that comes
into play because adsorption is only a surface process and
as consequence of mass conservation processes.
Adsorbate flows into the porous adsorbent to reach the
sites that are hidden more deeply in the particle; this leads
to the mass-transfer equation in solid. Assuming spherical
shape, the equation is
 
qq Ds q 2 qq
¼ 2 r
qt r qr qr
where Ds is the diffusion coefficient of adsorbate in the
adsorbent and r is the radius of the particle.
To simplify the solution of the system of the two mass-
transfer equations, the latter can be simplified assuming
that the solid particle also behaves as if a solid film was
present, that is,
qq
¼ ks ðqi – q Þ
qt
where ks is the mass-transfer coefficient in the solid, q is the
concentration of adsorbate in the solid volume (and not mass
as previously), and qi the concentration at the interface.
At the interface, adsorbate in fluid and solid are at
equilibrium, which, for simplicity and with the constraint
already mentioned, is assumed to be linear, that is,
qi ¼ mCi

Equalizing mass-transfer fluxes (no accumulation is

permitted at the interface), after several calculations it is
possible to describe the flux of adsorbate that sticks on the
surface with the following equation:
Porous
 – 1  – 1 
q
adsorbent
qq m 1 1 1
¼ þ ðmC – qÞ ¼ þ  C–
qt kf ks kf ks m m

Given the assumed linear equilibrium, the equation

can be rewritten as
 –1  –1
Molecular diffusion qq m 1 1 1
¼ þ ðq  – q Þ ¼ þ ðC – C  Þ
qt kf ks kf ks m

where q and C are the concentrations, respectively, on

Eddy diffusion
Figure 3 Conceptual model used to derive the equation of the
dynamics of adsorption: a stagnant liquid (or gaseous) film,
where only molecular diffusion occurs, surrounds a particle of
porous adsorbent immersed in a liquid (or gaseous) bulk where
concentration of solute is constant due to eddy diffusion.
solid and fluid at equilibrium.
Once again, like in absorption, the driving force of
global mass transfer is the distance from the equilibrium,
and the total resistance is equal to the inverse of the sum
of the inverse of single resistances.
64 Ecological Processes | Adsorption
Adsorption in Ecology
Elements cycle in the ecosphere following different
pathways through the different sphere: biosphere, hydro-
sphere, atmosphere, and lithosphere. These cycles play a
fundamental role in ecology because they permit, for
instance, the supply of nutrients to life, contribute to the
homeostasis of the system, and allow the continuous flux
of matter that sustains an ecosystem.
Adsorption is one important process that contributes to
the accumulation of the elements in the lithosphere:
thanks to this process dissolved compounds can be
trapped temporarily or permanently on solids where
they can stay inert or react with the solid matrix.
The cycle of phosphorus in the ecosphere is a good
example of how much adsorption is important in ecology.
Phosphorus is one of the five major constituents of all living
organisms, and one of the two (with nitrogen) that usually
can limit growth of primary producers (C, H, and O usually
being abundant). Hence, its availability is fundamental for
the maintenance of the ecosystem. Inorganic phosphorus is
usually present in the environment as orthophosphate
(PO34 – ) and its reduced forms HPO24 – and H2 PO4– that
are more common at environmental pH. Dissolved phos-
phates can be physisorbed and chemisorbed on soil. The
latter can occur through formation of a complex with metal
cations through hydroxyl groups, in particular with iron and
aluminum hydrous oxides (Fe(OH)3, Al(OH)3), or other
metal cations (e.g., Ca2þ in CaCO3). Another good matrix
is clay, and especially its aluminosilicates: in this case sorp-
tion occurs into the clay lattice replacing surface water
molecules or, at higher concentration of phosphates, silicates.
As a main result of this tendency to adsorption, phos-
phorus is mostly trapped into particulate and is not much
available in its dissolved inorganic forms. This is the
reason, for instance, why the main pathway to travel
from land to sea is connected more to solid transport
(e.g., erosion) than the liquid one (e.g., leaching).
Particulate P is not only less mobile than the dissolved
form, but also not, or little, bioavailable; this is one of the
reasons why it is more limiting than nitrogen even if the
amount necessary to living organisms is lower. In case of
deficiency of P, plants are able to boost desorption from
soil-changing environmental conditions.
Desorption can also occur without the boosting effect of
vegetation: in aquatic ecosystems, sediments can become
anoxic, for instance, as consequence of aerobic degradation
of huge amount of organic matter due to eutrophication of
the water body. In these conditions, P desorbs (e.g., due to
reduction of iron) and is released from sediments. The
amount released can be very significant, and even the
largest source of phosphorus in the ecosystem (e.g., in the
Baltic Proper) overshadowing in the short term the effect of
reduction policies.
Adsorption, together with ionic exchange, plays also
a key role in another important ecological process: acid-
ification. This is a natural process that consists of the
deposition of acid substances in the environment with
a series of relevant consequences on the ecosystems
(see Acidification). One of the elements largely responsi-
ble for acidification is sulfates, mainly coming from fossil
fuel combustion. After the deposition of sulfuric acid,
sulfates leach into the soil where they can be trapped
and stored, adsorbed mainly on the surface of Fe3þ and
Al3þ hydrous oxides. Furthermore, part of the acidic
compounds can be neutralized via ionic exchange using
metallic cations present on the soil like Mg2þ, Ca2þ, and
Kþ. Thus, the acidic anions are fixed in the soil and
acidification of surface waters is prevented or at least
reduced. At the same time soil ecosystem suffers several
problems. pH in the soil decreases, leading to an increase
of mobility of Al in porewater, that can be toxic for plants
if in excess. Furthermore, neutralization of sulfates ‘con-
fiscates’ important oligoelements for primary production:
if they become scarce, plants grow less healthy, and they
can also stop growing if the deficiency of these elements is
critical. Forests are usually the more affected because of
their higher needs of nutrients and longer life cycle.
Adsorption is not an irreversible process; hence, if
concentration of sulfates in pore water decreases (due,
for instance, to a decrease of deposition related to
improvement in abatement technology of emissions),
they can be desorbed and leach to surface waters. In this
case, the effects of a reduction of emissions cannot be
observed in a short term: this is the case of some
European catchments (mainly in the Central and
Northern Europe) with high sulfate storage in which no
reduction of release was observed despite the reduction of
emissions and deposition achieved in Europe.
Adsorption occurs not only on inorganic solid surface –
it concerns any kind of surface, even the cell membrane.
This is indeed the mechanism used by viruses to stick on a
cell and then inoculate their genetic information inside in
order to replicate themselves. Adsorption of viruses on
cell membrane is a two-step process: the first concerns the
contact and bond of the virus on some specific sites, called
receptors. The receptors are proteins that are able to bind
with other proteins that are on the virus surface (the VAP –
virus attachment protein). Adsorption bond between
receptors and VAP is mostly due to steric reasons, more
than electrochemical affinity. Despite the selectivity of
this bond, this is not unique: a receptor can attach differ-
ent viruses, provided with the same or morphologically
similar VAP, and larger viruses can be equipped with
more than one VAP in order to increase the probability
of infection. This step is still reversible: viruses can desorb
(especially at higher temperature) and move freely in the
environment looking for another cell to adsorb to. The
 Population Dynamics | Age Structure and Population Dynamics 65
second step is irreversible, and involves directly the struc-
ture of the virus.
Viruses adsorb not only on living cells, but also on
inorganic soil particles, such as sand or, especially, clay.
Several mechanisms have been proposed, all based on
electrochemical forces like van der Waals forces: the
bond can occur directly between anionic groups on
viruses and cations on clay, or between two anionic
groups mediated by water molecules. Adsorption on soil
plays an ecologically important role, not only because it is
a way to disinfect waters, but also because it is a good way
for transport of viruses, and then diseases (for animals and
also for bacteria or algae). Indeed, viruses adsorbed on soil
are more resistant to the different disinfectant agents, and
then their survival time increases. If the soil particles are
mobile, viruses can be transported (e.g., via runoff) in
other ecosystems where they can desorb from particles
and infect their targets.
Age Structure and Population Dynamics
L C Bender, US Geological Survey, Las Cruces, NM, USA
ª 2008 Elsevier B.V. All rights reserved.
Age Structure Effects in Age-Class-Structured Species
Age Structure Effects in Stage-Structured Species
Age structure in populations can take a variety of forms
and thus have a variety of effects on population dynamics.
Species can be comprised of multiple age classes in a
single-stage life cycle (hereafter, age-class structuring),
such as in most birds and mammals. Species can also
show multistage life cycles, where different stages in the
life cycle are analogous to age classes (hereafter, stage
structuring). Such life cycles are common in inverte-
brates, amphibians, and plants. Species can also show
both types of age structuring; typically, this involves a
stage-structured life cycle where the longest-lived stage
(usually the adult or reproductive stage) also shows two or
more distinct age classes. For example, trees have both
multiple life stages (seed, plant) and age classes within the
plant stage (i.e., seedling, sapling, mature tree). Both
age-class structuring and stage structuring in populations
can affect population dynamics, albeit typically at differ-
ent scales. Stage-structured populations are commonly an
adaptation to habitats that show extreme temporal or
spatial heterogeneity in resource availability. As such,
stage-structured populations generally have one or more
See also: Acidification; Enzymatic Processes.
Further Reading
Atkins PW and de Paula J (2001) Physical Chemistry, 7th edn. Oxford:
Oxford University Press.
Cooney DO (1998) Adsorption Design for Wastewater Treatment. Boca
Raton, FL: CRC Press.
Holtan H, Kamp-Nielsen L, and Stuanes AO (1988) Phosphorus
in soil, water and sediment: An overview. Hydrobiologia
170: 19–34.
Hüttling RF and Frielinghaus M (1994) Soil fertility problems – agriculture
and forestry perspective. The Science of Total Environment
143: 63–74.
Jobbágy EG and Jackson RB (2001) The distribution of soil nutrients
with depth: Global patterns and the imprint of plants.
Biogeochemistry 53: 51–77.
Prechtel A, Alewell C, Armbruster M, et al. (2001) Response of
sulphur dynamics in European catchments to decreasing
sulphate deposition. Hydrology and Earth System Sciences
5: 311–325.
Further Reading
life stages which can persist through long periods of
unfavorable environmental conditions or are capable of
rapid long-distance dispersal. When favorable conditions
return, these species can rapidly increase in numbers and
distribution (‘irrupt’) because of their high reproductive
potential. This allows these species to quickly colonize or
occupy all available ephemeral habitats. Such species are
usually defined by very high fecundity and display typical
r-oriented ‘boom or bust’ population dynamics in one or
more life stages. Examples of such stage-structured popu-
lations include many irruptive insect ‘pests’ such as the
eastern spruce budworm (Choristoneura fumiferana).
In contrast, age-class-structured populations are com-
prised of two or more age classes of individuals born at the
same time, or cohorts, in a single-stage life cycle. Often
age-class structuring can be complex, such as in long-
lived vertebrates which can have many age classes,
including newborns and multiple distinct subadult and
adult age classes. In contrast to stage-structured species
which show irruptive population dynamics to take
advantage of ephemeral habitats, age structure in