ELSEVIER

The Science of the Total Environment 167 (1995) 1-14

Physical weathering of stones

Dario Camuffo
National

Research

Council

CNR-ICTMA,

Padova,

Italy

Abstract
This paper reviewsthe main physicalagentsresponsiblefor stoneweathering.Particular emphasisis placedon the
effects of wind and water. Aeolian erosion occurs in windy regionswith sandy terrain, but in urban areas it is
extremelyrare and is often confusedwith other forms of deterioration. The problem of condensationon surfacesand
in pores is extensively discussed,in relation to pore shapeand size. Physicaleffects dominate in the smallestpores,
and solution effects in the largest ones. The Kelvin law and thermodynamic considerationsare used to explain
condensation-evaporationcycles and adsorption isotherms. Capillary rise, increase in pressurein air pockets,
freezing-thawing cyclesand micro meteorologicalconditions favorable for the soakingof monumentsare discussed.
A final section is devoted to the dissolutionof stonesand the formation of black crustsasa consequenceof the way
the stone is washedout or simply wetted by meteoric water. The intensity of rainfall is important in activating or
removing the dry pollutant depositsthat form on monuments,especiallyduring the dry periodscharacteristicof the
Mediterranean climate. Condensationplays a minor role comparedwith rainwater. However, the porosity, geometrical shapeand expositionof the stone are alsoimportant factors which can characterize different local balancesand,
consequently,the form of weathering.
Keywords: Weathering; Erosion; Condensation-evaporationcycles;Relative humidity; Mediterranean climate

1. Wind erosion
AIveolarization of stones may be due to several
causes, and is often incorrectly interpreted as
wind erosion. Apparently, the action of the wind
is very often involved: e.g. the formation of severe
pitting and interconnected, deep holes with loss
of granular material is very common in biocalcarenites (Fig. 1) where the rainwater dissolves
and weakens the bonds between granules, or the
wetting/drying
cycles favored by the action of
wind and solar radiation cause solution, mobiliza004%9697/95/$09.50
SSDI

tion and recrystallization of internal salts with the

consequent breaking down of the internal structure. At this point, any mechanical factor may be
responsible for the ultimate fall of the disaggregated granules. In particular, moisture is one of
the factors involved in the adhesive forces (interparticle surface forces and electrochemical forces)
acting on the independent granules (Fletcher,
1976). For these reasons the loss of material may
be visible on windy days when the wind reduces
the adsorbed moisture and the cohesion forces
and the turbulence favors the fall of the disaggre-

0 1995 Elsevier Science BV. All rights reserved.

0048-9697(95)04565-5

D. Camuffo /Science of the Total Environment 167 (1995) I-14

Fig. 1. Severe weathering of a biocalcarenite with loss of granules (Town Hall, Seville, Spain (Camuffo, 1994)).

gated granules in an unstable equilibrium.

Although the wind action is apparently involved in
this form of weathering, this is not wind erosion.
Wind erosion (also called corrasion) occurs
when abrasive particles impact with great energy
on a stone for long periods, causing extensive
micro mechanical damage which eventually results in macroscopic effects. The energy of the
particle is linearly proportional
to its density,
proportional
to the second power of the wind
speed and the third power of its diameter. Fine
particles follow the wind stream and fly around
obstacles without impacting on them, whereas the
coarsest particles, the inertial force of which is
greater than the viscosity of the air, can impact
with great strength on surfaces. However, when
the size of the particles is increased, the weight
increases also and the coarser grains cannot be
raised by the wind, so that there is an intermediate size interval where the grains are sufficiently
large to be dangerous, and can be swept by the
wind very short distances.
To this end, the particles can be divided into
the following four groups. The finest dust particles, with a diameter d < 100 pm, are airborne
and their main effect is soiling, not abrasion. In

the medium size range, i.e. 100 < d < 600 pm,
the granules are temporarily
lifted and fall in
successive leaps and bounds, so that these proceed
bY saltating according to the wind direction.
The height of the leaps depends on the roughness
of the soil, but on average this phenomenon only
affects the 1st m at the base of the monuments.
Particles with d > 100 pm cannot be lifted by the
wind and move by creeping and rolling. Particles
that are coarser than 6 mm cannot be moved by
the wind. Further details can be found in Bagnold
(1941), Pye (1987), Barndorff-Nielsen
and Willets
(1991).
In conclusion, only grains in the leaping range,
100 < d < 600 pm, are effective in terms of
erosion but only near the base of the monuments.
This weathering is important only in sandy, windy
regions and has been extensively discussed in the
case of the Great Sphinx (Camuffo, 1993) which
is situated near the border of the Giza desert,
Egypt. In this case, signs of severe corrasion actually appear at elevated levels of the monument,
i.e. between the mid-body and the neck. This
paradox is explained in that the Sphinx was eroded
when it was submerged (except the head) in the

D. Camuffo

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of the Total Environment

desert sand and corrasion occurred following the

changing levels of the dunes (Fig. 2).
Corrasion is extremely rare or unknown in urban areas. In general urban environments havent
many grains of a dangerous size and buildings
reduce the wind speed near the ground, except
for some narrow places where wind channeling
occurs; in addition, monuments are situated on a
base which is usually above the dangerous height.
The weathering that affects the base of urban
monuments is mainly due to frequent mechanical
collisions, capillary rise of rainwater, anthropogenic dissolved pollutants and animal urine
and/or other biological attacks; in cold regions
freezing thawing cycles are also important near
ground level.
2. Condensation
The water vapor becomes saturated at relative
humidity RH = 100% when the air (and therefore the moisture dispersed in it) reaches the dew
point. Cases of formation of droplets in the free
atmosphere, or condensation on a smooth or
porous surface, or inside internal pores must be
distinguished (Camuffo 1984a; 1988; 1991/1992).

Fig. 2. The Great

Sphinx

partially

submerged

167 (1995)

1-14

The problem of surface moisture and condensation is very complex, and depends on the
chemico-physical characteristics of both the atmosphere and the work of art. In the case of a
non-reactive, non-porous surface, condensation
occurs when the temperature of the stone surface
T, reaches, or drops below the dew point (DP) of
the air, i.e. T, I DP, irrespective of both the
degree of saturation of vapor (RH) and the temperature of the air at some distance from the
surface. Evaporation occurs when T, > T,, where
T, is the wet bulb temperature of the air. The T,
value distinguishes between the two processes
and determines, for example, whether a surface is
wet because it is cold (condensation) or it is
evaporating as a consequence of capillary rise.
Contamination
with soluble salts which raise the
DP may cause departures from this simple
scheme.
In the droplets, all the water is in a liquid state;
in porous bodies some water is absorbed and
bound (solid state), some is liquid and free.
In pores with a radius rp CK 1 pm the physical
effect dominates; in pores with an rp r 1 pm
and contaminated by soluble salts, the physicochemical effects which determine the equilibrium

in the desert

sand (photo

Donald

Mac

Leish).

D. Camuffo /Science of the Total Environment 167 (1995) 1-14

pressure for solutions may also cause condensation at lower RH, occurring typically in a marine
environment due to contamination with sea salts.
Further chemical details are neglected here as
this paper focuses on the physics of stone weathering.
Water supplied by condensation causes dissolution of the material
matrix. Condensationevaporation cycles cause migration of dissolved
salts and recrystallization
elsewhere, e.g. efflorescences and subflorescences, thus weakening
the material and causing loss of the aesthetic
value. Wet materials, e.g. rocks or mortars, may
have their mechanical resistance diminished. In
other cases, the presence of a film of water may
decrease the free surface energy of the material,
thus weakening it (Winkler, 1985).
In certain cases, e.g. clay minerals, water may
alter the structure of the material, causing expansion, stress and fractures. In fact, the crystal
structure is composed of a series of wafers and
positive ions are frequently trapped between the
wafers. Water is able to penetrate the crystal as it
is attracted by the hydroxy groups causing the
clay to swell. When the RH decreases, the adsorbed water evaporates, but the structure between
the wafers may have changed due to the formation of new crystals. The contraction leads to
hysteresis, and in the long run, adsorptionevaporation
cycles cause irreversible
damage
(Torraca, 1981).
Dampness and humidity favor biological life
and biological weathering; this negative phenomenon becomes greater and greater when the
duration, or the frequency, of the time of wetness
(TOW) increases. During the time in which the
stone is wet, chemical reactions occur between
the pollutants deposited and the stone (Laurenzi
Tabasso and Marabelli,
1992); the damage is
thought to be related to TOW, although no general formula has yet been found to link the damage to TOW.
Condensation is also responsible for increasing
the deposition rate of airborne pollutants. This
fact is due to two different factors: (i) the particles and the hydrophilic gases that impact on a
wet surface stick to it without bouncing, so that
the capture efficiency of the surface is increased;

(2) when condensation occurs near the wet surface several microphysical processes occur, the
ultimate result of which is the transport of gases
and particles towards the surface, as follows. In
the presence of condensation (or evaporation)
two opposite concentration
gradients of water
vapor and dry air are generated which cause two
opposing flows of water molecules and dry air.
These two flows exert opposing drags on the
aerosol particles, but the drag of the air molecules
dominates, having the mass (MN = 28 and MO
= 321 greater than the vapor molecules (M, =
18), so that net diffusive transport is generated in
the opposite direction to the pure water diffusion
(diffusiophoresis). On the other hand, the migration of dry air molecules by diffusion tends to
cause a pressure imbalance near the surface which
is immediately counteracted by the hydrodynamic
flow of the medium, called the Stefan flow. This
aerodynamic flow, which compensates for the
diffusive flow of dry air, is a micronic wind capable of transporting all the particles which arrive
near the surface, irrespective of the particle size:
it is so powerful that it overcomes the opposing
net phoretic force due to pure diffusion. In the
case of condensation, the Stefan flow transports
all the particles towards the surface; in the opposite direction in the case of evaporation. Generally, condensation continues for many hours, especially during night time, and solar radiation
causes the rapid evaporation of all the condensed
water. Therefore, deposition is favored for a long
period time, and is followed by a short period
when deposition is prevented by the opposing
Stefan flow during evaporation. Thermophoresis,
i.e. the transport of particles towards a surface
that is colder than the air, or vice versa for a
warmer surface, can, like the Stefan flow, at times
aggravate the effects of other deposition processes
or even oppose them to such an extent that the
overall rate of deposition is, at times, greatly
reduced.
3. Droplets and pores
Inside the wet pores, or in the presence of
suspended droplets, saturation is not reached at

D. Camuffo

RH = lOO%, which
rium with a plane
equilibrium
with a
computed by means
In (RH/lOO)

/Science

of the Total Environment

is in thermodynamic equilibwater surface. The RH in

spherical water meniscus is
of the Kelvin equation,

= (2crV,/rRT)cos8

where the radius of curvature r of the water

meniscus is the main parameter; cr is the water
surface tension; V, the molar volume of the
liquid adsorbate, i.e. 18 cm3; 0 the contact angle
with the solid surface (if any; case is positive for
wettable surfaces; negative for hydrorepellent
ones); R the gas constant and T the absolute
temperature. The formula can be rewritten for
any shape of meniscus, by substituting instead of
2/r the ratio of the incremental values dS/dV of
the meniscus surface dS and the related volume
d?J; e.g. dS/dV
= 2/r for a sphere; dS/dV =
l/r for a right circular cylinder or a circular torus
(where r is the radius of the cylinder or the
generating circle, respectively); dS/dV
= 3(2r2
+ h2)/(rZh ,/(r2 + h2)) for a cone of height h. In
this paper only the simplest case of spherical
geometry is considered.
In the case of pure water, the Kelvin formula
states that the logarithm of the RH in equilibrium with the meniscus is inversely proportional
to the radius of curvature of the water surface.
Higher RH levels cause condensation, and lower
RH evaporation. The vapor tension of a solution
is lower than that of pure water. In the presence
of hygroscopic salts, condensation is anticipated
and the equilibrium RH for a spherical meniscus
can computed by means of the following two
formulas:
In (RH/lOO)

= ((20; M,/p,rRT)
-( p,/p,Ml

In (RH/lOO)

+ in,/n,))cosO

= ((2a;M,/p,rRT)
-im,M,,I:

p,M,)cos8

where the labels s and w refer, respectively, to

the solute or water, M is the molar mass, V, the
actual volume of the solute, i a parameter closely
associated to the VantHoff coefficient for solu-

167 (1995)

l-14

tion and depends on the molality, IZ the molar

fraction and m, the actual mass of the solute.
In the case of atmospheric processes such as
the formation of droplets in a cloud or fog (Mason, 1971; Pruppacher and Klett, 19801, the system is composed of spheres of water floating in
air, and the radius of the droplets is positive, i.e. r
> 0 for a convex water surface. In this case
supersaturation is required for equilibrium
with
the curved water surface, i.e. RH > 100% and,
consequently, T < DP. The smaller the droplet,
the greater the supersaturation
necessary for
equilibrium.
For this reason, droplets may only
form by adsorption of water on some condensation nuclei which, when water vapor condenses
upon them, form solutions on which the equilibrium vapor pressure is relatively low. In other
words, the depression formed by the chemical
solution compensates for the overpressure generated by the convex meniscus of the droplet, so
that condensation occurs and the droplet grows.
On porous materials, however, when water
starts to wet the inner cavity of the pores, the
situation appears complementary
to that of the
droplet, as the air pockets in pores can be considered to be approximately spheres of air with
water outside them and the radius of curvature is
negative, i.e. r < 0 for a concave meniscus. The
RH required for equilibrium
with a negatively
curved surface is lower than the RH = 100%
required for saturation in the atmosphere (Fig. 3).
In the pores, saturation is anticipated at RH <
100% and at a critical temperature of T, > DP,
making condensation easier. Condensed water
may be found in micropores under usual conditions, but also in relatively dry environments.
The individual pore characteristics affect the
weathering of stones. Total porosity, total pore
surface, spatial association of pores that may form
pockets and necks, pore size, pore form and pore
radii distribution are important variables. Stones
are characterized by a wide variety of pores and
necks, with different shapes and sizes, which range
from angstroms to millimeters and can be classified into several classes, depending on their
properties based on laboratory analysis (Fitzner,
1993). The porosity may change with time, espe-

D. Camuffo /Science of the Total Environment 167 (1995) I-14

60
Q

70

60
50
40

0,001

0,Ol

O,l
r

(w)

Fig. 3. Relative humidity RH (%) in equilibrium with a concave meniscus of water with radius r ( pm), according to the
Kelvin law. C, cylindrical meniscus; S, spherical meniscus.

cially in the subsurface layer where migration of

salts, leaching, dissolution, erosion and other
physical, chemical and biological attacks occur
(Biscontin et al., 1993).
Open pores, with very large outlets compared
with the pore volume, are typically found on the
surface of bodies. The typical shape is that of a
hemisphere, or a portion of a hemisphere (Fig.
4a). Open pores behave symmetrically with reference to droplets suspended in the atmosphere:
the smaller the pore, the lower the RH required
for equilibrium with the water meniscus. For each
open pore, condensation begins at a low critical
RH, determined by the radius of curvature when
the RH increases, by keeping the radius of curvature of the meniscus (r,) in equilibrium with the
variations in RH. An increase in RH corresponds
to an increase in both condensed water and in r,,,
and vice versa. The hemisphere is completely
filled at RH = 100%. All the steps in this process
occur in equilibrium with RH and the process is
reversible.
Internal pores, with small outlets, are typically
found inside bodies (and connected to the atmosphere by a small hole facing the surface or
entering other pores or capillaries, Fig. 4b) and
they behave in a different manner. When condensation begins at the low critical RH, the con-

Fig. 4. (a) Condensation in an external pore; (b) condensation

in an internal pore.

densed water deposits in the small volume of the

pore, reducing the free surface of the meniscus
and the radius r,,,. After a short time, when some
condensation has occurred, the smaller the new
radius r,,, the lower the equilibrium
RH, so that
the actual RH inside the cavity, which was in
equilibrium with the former rm, now corresponds
to supersaturation for the new smaller r,, and
the process is accelerated. Therefore, the RH
calculated by using the radius of the pore (TJ in
the Kelvin formula, i.e. RH(r,), is no longer a
neutral equilibrium
value, but a critical value of
unstable equilibrium
which triggers off the complete filling of the pore. As a consequence, the
process is now irreversible.
According to the Kelvin law, condensation occurs first in necks, which are the cavities with the
smallest radius of curvature. When the necks are
filled with water, air-pockets remain entrapped in
the pores and further condensation is impossible

D. Camuffo /Science of the Total Environment 167 (1995) 1-14

in steady state conditions. Internal condensation

may only continue when variations or fluctuations
in temperature or atmospheric pressure cause the
displacement of the water inside the pore necks.
Nocturnal cooling of the body may reduce the
pressure inside the pores and cause the water
condensed in the neck to be sucked into the pore.
According to Cantors law, the required excess
pressure is inversely proportional
to the neck
radius. When the excess pressure is sufficient,
plugs of condensed water can be pushed out and
trapped inside the pores, or can be forced to
migrate into the material. Condensation may continue by means of these steps, so that the amount
of adsorbed water is also a function of the pumping efficiency of these variations.
Similarly, evaporation from an open pore starts
from its outlet, removing water from the pore and
increasing the radius of the free meniscus. The
equilibrium
RH given by the Kelvin formula becomes accordingly greater and greater, so that the
actual RH becomes lower and lower in comparison with the value required for equilibrium.
Evaporation continues until1 all the liquid water
(i.e. all the water inside the pore, except the first
and second molecular layer in contact with the
surface which is attached with a stronger ice-type
bond) has evaporated. Evaporation is triggered
off when the RH exceeds a critical value which is
calculated from the radius of curvature of the
pore outlet (r,). As this critical RH(r,) is lower
than all the values in equilibrium with the intermediate steps when the meniscus increases its
radius during evaporation, this process is also
accelerated and is irreversible.
The condensation-evaporation
cycles being
thermodynamically
irreversible present noticeable
hysteresis as condensation occurs when triggered
off by RH(r,) and evaporation by RH(r,). In
practice, RH(r,) and RH(r,) are not just two
precise levels of RH, but two ranges, determined
by the actual distribution
of rp and r, in the
porous material.
When the temperature of the stone drops below
freezing point, freezing-thawing cycles develop,
and the pressure exerted by the ice crystals may
have disruptive effects. Of course, the greater the
size of the pores the greater the force, so that

damp stones characterized by large pores and

high total porosity are more likely to be damaged
(Fitzner, 1993). However, Torraca (1981) noted
that in the Mediterranean
climate the damage by
frost is more likely to occur in materials which
have a prevalence of small pores, i.e. with size
between 0.1 and 1 pm. This paradox is explained
by the fact that in a non-humid climate the small
pores have the largest probability of being filled
with water at intermediate RH values, due to a
combined action of the Kelvin law, solution effect
and adsorption hysteresis. In addition, the Kelvin
law can be adapted to the vapor-solid
and
liquid-solid
changes of phase. The result is that
small curvature radii are associated with deep
freezing point depressions.
4. Adsorption isotherms

The condensation-evaporation
cycles can be
represented by the so called BET (Brunauer,
Emmett
and Teller)
adsorption
isotherms
(Brunauer, 1945; Gregg and Sing, 1967; M&hail
and Robens, 1983), in which the amount of adsorbed water, WA, is plotted against RH. In practice,
this kind of graph shows the weight increase due
to the adsorption of water by an initially dry
sample of material when the RH increases from 0
to 100% and then decreases again to 0%. The
most common type is composed of three branches.
The first branch, characteristic of the very low
RH, occurs when all the stone surface, both external and internal (i.e. the visible surface and the
surface in contact with the air, but inside the
pores), is progressively covered with a layer of
water in the solid state (i.e. strong bonding with
the internal surface of the pores), with a final
thickness of two or three molecular diameters. In
this branch the graph of the adsorption is coincident with the desorption one. The condensationevaporation process is characterized by a one-toone correspondence and is reversible depending
linearly on changes in RH.
In the intermediate RH range, after the total
surface has been covered with this solid layer, a
further increase in the RH leads to the formation
of bulk, liquid water in the internal pores. This

D. Camuffo

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of the Total Environment

second branch becomes steeper and steeper as

the pores are filled by water. In every pore with a
radius r-r, condensation occurs when triggered by
RH(r,) or by the chemical effect. If all the pores
have the same size the condensation branch is
very steep. In this branch the process is no longer
reversible: if the RH decreases in this branch
some minor hysteresis loops start.
The third branch is characterized by very high
RH, when all the internal pores are filled with
water. In theory, this branch should be horizontal,
as no further increase of WA is possible, also
because when RH = 100% the surface is in
thermodynamic
equilibrium
with the same number of molecules condensing and evaporating. In
practice, this branch is tilted because the spectrum of the pores is wide and before reaching RH
= 100% there are always some large pores which
are empty and which become progressively filled.
In addition, the presence of contaminants or soluble salts causes the condensation to occur earlier,
so that the environment is in a situation of supersaturation and condensation occurs, forming liquid films or droplets on the external surface. A
similar condition of supersaturation occurs when
the surface temperature drops below the DP, so
that at the interface between the stone surface
and the air the RH is > 100%. In any case, the
amount of liquid water that can adhere to the
external surface is modest, and the final branch is
slightly tilted, with a sharper rise near the upper
extreme due to the solution effect. If condensation stops before the droplets fall from the damp
stone, this branch is again characterized by a
one-to-one correspondence and is reversible.
On lowering the RH, the process first develops
along the last condensation-desorption
branch,
until1 the external water has evaporated. Continuing to lower the equilibrium
RH after all the
pores have been filled with water, evaporation
may proceed, emptying the pores and this may
occur only when triggered by RH(r,). If RH(r,)
< RH(r,) a hysteresis loop is generated, the
condensation branch being linked to the size of
the internal pores rr; the evaporation branch
reflects the dimension of the outlet of the pores
r,,. If all the pores have the same outlet the
evaporation branch is very steep. The derivative

167 (1995)

l-14

of the amount of water WA which is adsorbed in

the stone by varying RH, i.e. dWA/dRH,
shows
peaks corresponding to the dominant features of
the pores. These peaks are narrower or broader
according to the distribution of the dimensions of
the pores and their outlets. After all the internal
bulk water has evaporated, lowering the RH, layers of solid water (first branch) start to evaporate,
but with a much greater latent heat (e.g. 2 or 3
times greater) than the evaporation heat in the
liquid-vapor transition.
Cycles involving the last branch mobilize the
salts on the surface and subsurface layer; cycles
involving the hysteresis loop dissolve and re-crystallize the soluble salts at a deeper layer and
cause outward migration with the formation of
new efflorescences. The mechanical stress that
follows thermohygrometric
changes in a structure
weakened by long term dampness may have dramatic consequences. In addition to the chemical
deterioration,
the presence of water inside the
pores favors biological epilithical and endolitical
life, and biological weathering. Saturated environments should be carefully avoided.
5. Penetration

of rainwater

Penetration of rain water into the monuments

while it is flowing over the surface also depends
on climatic factors, in addition to the nature of
the material (Dullen, 1979). Penetration into capillaries and porosities is possible only when the
whole surface (i.e. both external and internal
ones) is covered by a single or double layer of
water molecules in the solid state, and this process
is not possible when the surface is completely dry,
i.e. not covered with these layers of solid water
(Camuffo, 1991b).
When the surface of the material is still wet,
i.e. covered with the monolayer of solid water, as
generally occurs in the more humid climates, liquid water penetrates by simply advancing towards
the interior with a concave meniscus that does
not experience any change in the curvature (no
external work due to surface tension); in addition,
the concave meniscus forms a lower vapor pressure in front of it, which favors penetration into
the capillary (positive work).

D. Camuffo

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of the Total Environment

In the case of a completely dry surface, without the solid water monolayer, the meniscus of
the water penetrating into the capillary is convex
in the forward direction, and the meniscus must
elongate gradually as the water penetrates into
the capillary. The work required against the surface tension and the higher vapor pressure over a
convex meniscus is so great that water can not
penetrate under such conditions and runs over
the monument without dampening it. For dry
materials a preliminary
wetting of the internal
surface is a necessary condition for water to penetrate and soak into it.
In a hot, dry climate which is predominant
during the summer in southern Europe, the external and internal surfaces of monuments are completely dried out because of the warming associated with strong solar radiation. This then means
that water, from a typical sudden shower in the
afternoon, can not initially penetrate into the
pores and capillaries of the stone, because these
are not lined by a monolayer of water molecules
in the solid state that would allow for the liquid
water to run over it.
Pressure fluctuations associated with wind gusts
may cause pressure differences between the interior and exterior of the monument, which may
force the water running over the surface to penetrate into the cavities and be trapped in the pores.
With successive steps, water may arrive at the
interior of the porous materials. External pollutants may also be trapped inside the material and
continue the deterioration process each time microclimatic factors are suitable.
6. Capillaries

The amount of water adsorbed varies linearly

with the square root of the time t, i.e. WA = kJt,
where k depends on the characteristics of the
material, although some exceptions have been
noted (Gummerson et al., 1980); if there is divergence in the water flow with lateral spreading of
the water front, the cumulative water adsorption
increases more rapidly than ,/t, (Hall, 1981). Capillary suction occurs with the progressive displacement of water, so that it cannot be stopped by
pockets of air entrapped in the pore and capillary

167 (1995)

l-14

system, except for ducts without an outlet, in

which the capillary pressure is counteracted by
the entrapped air. Capillary suction (in particular
for ground water or collected rainfall) is therefore
much more efficient than condensation in causing
dampness.
Overpressures generated by heating are important, e.g. on porous tiles where the cavities are
topped by the glaze of the decorative ceramic
surface, especially when the thermal shocks are
noticeable. Capillaries closed at one extreme may
be filled with water until1 the pressure of the air
entrapped equals the pressure II = - 2 a/r determined by the meniscus curvature (the Laplace
law) minus the contribution due to gravity p =
pgh, where p is the pressure, g the acceleration
of gravity and h the height of the water column
(the Stevin law). Solar radiation falling on the
material with embedded air pockets causes an
increase in the pressure inside the cavities due to
the temperature rise AT according to the law of
gases, pV = (n, + n,) RT, where V is the
volume, II, and n, the number of moles of dry air
and water vapor, respectively. This overpressure
causes the water meniscus to retreat and reach a
new equilibrium
due to the simultaneous presence of a gas and a saturated vapor, as follows: (i)
II, is constant and the partial pressure of dry air
is inversely proportional to V; (ii> n, is not constant and is independent of V; in fact, AT causes
a decrease in RH and consequently new water
molecules can evaporate until1 the original RH is
re-established, being the RH determined by the
radius of the capillary, here supposed unchanged
(Camuffo, 1991a). The partial increase of pressure due to the vapor is shown in Fig. 5.
Of course, the damage may be enhanced in the
presence of soluble substances, osmotic effects
and salt crystallization. On plasters and frescoes,
at high humidity, residual crystals of calcium oxide may hydrolyze becoming calcium hydroxide,
causing pitting as a consequence of its growth.
Crystallizing salts have a disruptive effect as a
consequence of the pressure generated by the
growing crystals, hydration or thermal expansion.
The osmotic effect causes an upward rise of the
ions that displaces the wet front upwards. In the
region where water evaporates, the transported

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0
0

10

15
t

20

25

30

("0

Fig. 5. Increase in partial pressure p(t)/p(O) of the water

vapor following a temperature rise t (0 in a capillary due to
both the vapor heating and the increase of the number of
water molecules which had evaporated to re-establish the
original RH in the cavity. Note that p(t) is not affected by a
retreat of the water meniscus and an increase in the volume of
the cylindrical air pocket, the molecules being a saturated
vapor and not a perfect gas.

salts accumulate locally causing more and more

damage (Arnold and Zehnder, 1990).
7. Rainfall

and crusts

Chemical weathering is not directly related to

the concentration of pollutants in the air, but to
the combined action of the pollutants deposited
on the monument surface, when microclimatic or
meteorological
factors may trigger some deterioration processes. Air pollutants may be deposited either in the dry phase or in the wet one,
and wet deposition is the result of the atmospheric scavenging occurring in clouds, when the
droplets are forming and growing (rainout), and
during the fall of the droplets (washout).
The amount of pollutants which is deposited in
the dry phase is the result of the concentration of
airborne pollutants, the velocities of the different
microphysical transport mechanisms near to and
at the interface between the air and the artifact
and the capture efficiency of the surface itself. It
denotes the net fraction of the atmospheric pollutants that are ultimately deposited on the monument and that may react with it. A measure of the
pollutant concentration in the atmosphere with-

167 (1995)

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out an estimate of the deposition velocities solves

only a part of the problem.
Rainfall transports acid substances from the
atmosphere to the surface of monuments. However, the purely meteorological nature of the precipitation is also of very great importance. In the
Mediterranean climate it does not rain frequently
in summer, and a great quantity of pollutants is
deposited in the dry phase. The same occurs in
winter in regions which are under the influence of
the ridge of high pressure that connects the Russian high with the Azorres anticyclone. Under
these conditions, the dry deposition that occurs in
urban sites is much greater than wet deposition.
If precipitation
occurs in the form of a heavy
shower, the dry deposit is washed away quickly.
Thus, knowing the intensity of the rainfall (i.e.
amount/day)
may be more useful than the total
monthly water precipitated.
The frequency of
rainfall may be even more useful in giving the
first indication about the possible dominance of
wet or dry deposition.
Although the acidity of the rain as well as the
turbulent character of the run-off attacks the
stone, this is not as damaging as drizzle which
wets the surface making the dry deposit chemically reactive without removing it. Under these
circumstances, the pH of the rain may be of little
importance in comparison with the acidity of the
dry deposit which generally contains elevated
quantities of both acidic pollutants and catalysts,
such as oil-fired carbonaceous particles (Camuffo
et al., 1984; Camuffo, 1986).
Acid water acts by both dissolving the stone
surface and the cement that binds granules to
each other. In the latter case modest dissolution
is sufficient to cause the loss of many granules
resulting in erosion. This rate of erosion may
exceed the rate of dissolution by a factor of N 2
for marble and 3 for limestone (Beadecker and
Reddy, 1993).
Many sulfation and dissolution processes occur
especially in stones which have a calcareous matrix, metals are corroded, external frescoes and
murals are lost. However, even in those cases
where the particles deposited on frescoes or murals are not subjected to direct wetting by rain
drops or run-off, an opaque layer is still formed,

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resulting in soiling. This, in turn means that the

picture becomes less clear, so that each time a
work of art is cleaned, it is subject to a degree of
stress brought about by the very nature of the
intervention. The formation of crusts is related to
the presence of water, but the necessary amount
is generally supplied by rainwater, which is larger
than that locally adsorbed by means of fog or
condensation. These processes involve an amount
of water < 1 mm/day which is very small when
compared with rainfall, which can be several tens
of cm/day. However, indirect action is possible:
condensation on non-adsorbing, external surfaces
may continue for some hours and form droplets
which eventually form descending rivulets. The
water collected at the base of the vertical surface
is supplied by a relatively large area and may then
be adsorbed by capillary suction, which is much
more effective (Bernardi et al., 1985).
The visual features of the crusts of marble or
limestone monuments is not only a function of
the prevailing
micrometeorological
conditions
near the monument, but also of the geometry of
the surface and its exposure to rainwater. Similar
geometries induce similar patterns of crusts. The
pattern of the white and black crusts found on
monuments is caused by the way meteoric water
wets or washes the surface: where run-off dominates, dissolution and erosion occur and calcareous rocks form white areas. These areas are characterized by crystals of reprecipitated calcite that
form when the rainwater with the dissolved stone
evaporates (Fig. 6); where the stone is wetted but
not washed out, black gypsum crusts originate
(Fig. 71, with embedded carbonaceous particles
which play an important role in this process.
Field observations (Camuffo et al., 1982; 1987;
Camuffo, 1984b; 1986; 1990) have shown that, in
the zones exposed to run-off, gypsum crystals
were found only rarely, whereas a thin layer of
spatic calcite crystals due to reprecipitation
was
common. On the other hand, the maximum quantity of gypsum was found where run-off was prevented, i.e. in the black crusts. The acid rain
hypothesis alone is not sufficient to explain the
main phenomenon due to sulfation, i.e. the black
crusts, which are one of the main problems affecting marble monuments. By the way, the gyp-

167 (1995)

1-14

Fig. 6. Example of a white area in a zone over which

rainwater runs-off. The surface has been worn away and
covered by reprecipitated crystals of spatic calcite. The pitting
is due to the biocorrosion of microflora in the past (Trajan
Column, Rome, (Camuffo, 1994)).

sum crusts due to simple sulfation by acid rainwater should be whitish, and not black.
The visual features of the deterioration
patterns could be related to the three main ways the
water wetted the surface: (i> run-off is associated
with white areas in the zones where the surface
had been worn away; (ii) damping due to splashing droplets, or percolation near zones where
run-off was present, is associated with black areas
where black crusts dominate; and (iii) absence of
both run-off and percolation, but possible condensation is associated with gray areas where
the stone was not chemically affected but covered
instead by a layer of dust and particles.

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Fig. 7. Black CIUUZits

deposit by means of running-off (Altare della Pa&a, Rome).

Although the specific mechanisms involved are

still under discussion, fly ash, microsoot and single carbonaceous particles (formed during the
combustion of oil) are active in forming black
crusts when they are wetted by the percolation of
rainwater. These combustion products contain
sulfur compounds and catalysts, and nucleate gypsum crystals when wetted, so that they become
embedded in a gypsum crust. The gypsum partly
results from the transformation of the underlying
rock, and partly from particle nucleation. The
black crusts have a dendritic appearance as a
consequence of the mechanism whereby the particles are deposited and bind together and with
the gypsum crystals; the proportion of the gypsum
and the airborne deposit determines the mechanical strength of the crusts. Where the underlying
substrate is not marble or limestone or the calcareous rock cannot be sulfated, the gypsum is
very scarce (i.e. only that originated by the particles) and the crust is very friable. All the black
crusts examined, samples of which were taken
from many European countries, contained carbonaceous particles and it has been possible to
reproduce this mechanism in the laboratory (Sabbioni et al., 1993). Of course, these dendritic

167 (1995)

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to 1remove

the

crusts cannot be confused with the black patches

of biological
origin (e.g. lichens, algae), with
growth, combination and repetition of some elementary structures, possibly associated with biocorrosive pitting. In particular, the microflora also
needs special microclimatic conditions to develop;
chiefly a frequent supply of water. For this reason
black biological patches can be found in places
where the formation of crusts composed of soot
and gypsum is impossible due to the frequent
presence of water.
Although the white areas are also subject to
dry deposition, the abundant run-off washes over
the monument surface and in general removes
most of the attached pollutants. Their action is
modest but is, however, continued by the falling
rainwater. The result is a modest wearing of the
surface which is only slightly dissolved and over
which crystals of calcite may reprecipitate.
When the stone is characterized by larger pores
and is absorbent, the visual features are quite
similar. Vertical
surfaces absorb the falling
droplets and run-off can not develop, so that the
dry deposit is not removed and may be transported
into the pores. Wash-out and dissolution may
only occur where great amounts of water are

D. Camuffo /Science of the Total Environment 167 (1995) I-14

13

Fig. 8. Visual features of a porous calcarenite wetted by splashing raindrops (the gray wall), dissolution by run-off where rainwater
may collect and run-off with turbulence (the white area below the window) and in a laminar regime after adsorption, releasing the
material previously removed (the darker gray area below the dissolution area) (The Mayors Palace, Brussels).

collected, e.g. under windows. However, the running water is eventually absorbed by the porous
stone; the running layer thins and thins, the turbulence damps, the flow becomes laminar and
then disappears (Fig. 81. In a turbulent regime the
surface is cleaned and thinned; in the laminar
one the material removed from the upper surface
is released onto the underlying rock. When the
regime is laminar, the first layer in contact with
the surface becomes saturated and is then chemically inactive. When it is turbulent, the chemically
active solution continually changes on the stone
surface which is subjected to heavy dissolution
and erosion due to loss of granules.
Acknowledgements
This paper presents scientific results of studies
supported, at different times, by the Commission
of the European Communities,
DG XII, STEP
Programme (Contract no. CT90-0107-SSMA) and
CNR (Comitato Nazionale per la Scienza e Tecnologia dei Beni Culturali). Thanks are due to
Dr. Adriana Bernardi for many useful discussions.

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