Section 4:

STONE MATERIALS:
Alteration and weathering

1
 Evolution of stone materials over time
Alteration processes of materials (in general, not only for stone materials)
are the NATURAL and “PHYSIOLOGIC” evolution of thermodynamic
systems that evolve over time according to more or less rapid kinetics
depending on the ENVIRONMENTAL CONDITIONS.

Result: formation of more thermodynamically stable substances or phases

( with lower energy) in comparison to the starting ones.

There are 3 types of weathering, that often occur simultaneously:

● PHYSICAL WEATHERING

● CHEMICAL WEATHERING

● BIOLOGICAL WEATHERING

Note: surface-treated stone materials (e.g. decorations and sculptures)

have a higher surface to external environment they are more
2
susceptible to PHYSICAL and/or CHEMICAL attack.
 Natural weathering of rocks

Both rocks in their natural state or in situ (e.g. in quarries) and used as
building or ornamental stone materials by man are subjected to
WEATHERING PROCESSES.

In general, weathering mechanisms are similar in both cases.

IMPORTANT

It is ALWAYS necessary to consider the so-called BOUNDARY (or

WORKING) CONDITIONS ( environment, climate) in order to:

● forecast the most likely weathering mechanism

● understand whether one particular mechanism of weathering is more

critical/dramatic/likely in comparison to the other ones
3
SOME PRELIMINARY CONSIDERATIONS:

● Alteration does NOT necessarily involve weathering: you might have only a
chromatic alteration, that is aesthetic but not functional or structural.

● The stages leading to the formation of sedimentary rocks (degradation of pre-

existing rocks, transportation…) can be considered as natural processes of
WEATHERING!

● For rocks in quarries, weathering caused by pollutants in the atmosphere (e.g.

acid rains) is significantly lower than that of exposed rocks (in natural state or
used as building/decorative materials)

● For rocks in polar environments, physical weathering is predominant (gelivity,

effects of thermal changes and shocks de-cohesion of crystalline grains)

● For rocks in tropical environments, chemical weathering is predominant (key

role played by water)

● “Cooking” of marbles in old unexploited quarries: due to repeated thermal

cycles (thousands and thousands of times), we have de-cohesion of calcite grains
and subsequent fracturing along the grains boundaries (not inside the grains)
4
loss of workability and mechanical resistance.
 Physical weathering of stone materials

● Micro-traumas during processing: due to mechanical SHOCKS we have

the formation of surface micro-cracks preferential points for the onset of
cracks that propagate inside the material and allow water access

● Coupling or contact with other stone materials or, for instance, with the
iron/steel bars in outdoor claddings effect of the different thermal
expansion coefficients (α)

● Too high loads/solicitations acting on the stone materials (e.g. wear in

paving/flooring, weight of the overhanging slabs in outdoor claddings)

● Wind and water effects: erosion, removal of exposed parts, wear

● Light effects: chromatic changes on the surface (oxidation reactions)

● Thermal shocks effects (sudden or relevant day-night thermal changes,

freezing-thaw cycles)
5
 Types of physical weathering
DISINTEGRATION
Detachment of powders or ultrafine fragments

DETACHMENT (in general)

Separation of layers either of different materials (e.g. the stone from the mortar or
plaster that support it in the claddings), or inside the same material ( in this case we
have exfoliation or flaking)

EXFOLIATION
Detachment of thin laminar portions (sheets)

FLAKING
Detachments or irregularly-shaped parts with relevant thickness (flakes)

EFFLORESCENCE
Salts formation on material surface; if inside or underneath sub-florescence

SWELLING
Localized lift

FRACTURING or CRACKING 6
Material separation that involves the displacements of the separated parts
 Effect of temperature

Continuous and sudden temperature variations (THERMAL CHANGES) can

induce mechanical stresses: different thermal expansion coefficients
dimensional and volumetric variations (shrinkage or expansion).

We can have the following temperature-caused phenomena:

● disintegration

● flaking

● exfoliation

● swelling.

Synergistic effect of T and water weathering due to GELIVITY

7
 Effect of water (1)

Water can interact with stone materials in all its 3 states: solid, liquid, gas.

Water is the major agent involved in physical weathering, and plays a key
role in the chemical one.

Water can come in contact with stones as:

● rain or other precipitation (fog, snow)
● humidity (air condensation)
● loss from hydraulic plant of buildings

WATER IS DRAMATICALLY DANGEROUS FOR HIGHLY POROUS

STONE MATERIALS

WEATHERING PHENOMENA DUE TO WATER:

● washing away (slow process of material removal and erosion)
● salt crystallization salt sub-florescence and efflorescence
● alveolization (creation/enlargement of pores + material detachment)
8
 Physico-chemical combined effect: T + water
WATER EFFECTS
THERMAL CHANGES
dissolution
sudden temperature
infiltration
variations possible re-precipitation (e.g.:
white coating of CaCO3)

Washing Salt
Rocks are bad heat efflorescence
away
conductors
Salt sub-florescence

GELIVITY
Surface hot,
Volume variation
inside cold
(e.g.: sodium sulphate
crystallized salt increases its
own volume (with respect to the
Mechanical stresses solubilised salt) of 300%!)

disintegration, flaking,
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exfoliation, swelling
 Malanaggio stone from Val Chisone (gray
gneiss) showing a tyoical “bowl-like”
weathering: swelling and flakes
detachment, together with light stains
and dark coatings (Chiesa della
Misericordia, Torino)

Royal Palace of Torino:

Skirting boards in Malanaggio stone
(gneiss) affected by exfoliation
10
 Effect of water (2)

WATER ACIDITY accelerates the processes of chemico-physical

weathering from a geologic time-scale (millions of years) to a historical
time scale (hundreds of years)

Example: it has been estimated that, during 40 years of exposition to highly

acid rains (pH < 4), the thickness of a microcrystalline marble can decrease
of 1.5 mm!

Natural pH values of water precipitation: pH = 5.6-5.8

If pH ↓ ACID DEPOSITIONS

(Not only acid rains: we should take into account all water-based
precipitations, including fog and snow apart from rain!)

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 Chemical weathering of carbonatic rocks

There are 3 mechanisms of chemical weathering for CaCO3-based rocks:

a) (bi)carbonation
b) nitrification
c) sulfation

a) CALCITE (BI)CARBONATION

I stage: dissolution in CO2-rich water of carbonatic stone materials (e.g.:

limestone, marbles, conglomerates with calcitic binder):

CaCO3 + H2O + CO2  Ca(HCO3)2

soluble BICARBONATE
If WATER ACIDITY is high (namely CO2 ↑), the EQUILIBRIUM tend to “shift” to the RIGHT

II stage: Ca bicarbonate dehydration (due to ↑ T) and CaCO3 re-precipitation:

Ca(HCO3)2  CaCO3 + H2O + CO2

dusty and incoherent appearance; it tends to detach (white coatings), or is 12
incorporated in hard and tough crusts
 Column basis (plinth) in Gassino stone from Basilica di Superga: high
weathering with flaking and
fractures.

Disintegration of Gassino stone with

detachment of surface portions, maybe
also due to the effect of weakening
induced by bush-hammering (columns
from Basilica di Superga)

Combined effect:
erosion by atmospheric
agents (wind, rain)
+
Calcite dissolution caused
by water 13
Appearance of “Macchia Vecchia Svizzera” just after extraction: nice polychromy

Relevant weathering of “Macchia

Vecchia Svizzera” in the columns of the
botanic garden at UniTO

The rock dissolves as it contains

veins of carbonatic (CaCO3)
cement dissolution
mechanism due to leaching
water (formation of soluble
bicarbonate etc.)

14
 Serena stone (sandstone
containing quartz, feldspar, mica
and calcite) has been widely used
as material for building in Tuscany
and, especially, in Florence

This stone undergoes significant

weathering due to the action of
atmospheric agents (e.g.
disintegration, exfoliation,
fracturing).

Rock de-cohesion is promoted by

the presence of mica flakes and by
calcite dissolution in water.

Pillar in Serena stone from “Basilica

della Santissima Annunziata” (Florence)
characterized by exfoliation and
chromatic alteration (from grey to
brown). 15
Lion in Serena stone (19th century) in front of Saint Pancrazio Church, Florence

Dramatic physico-
chemical weathering
of Serena stone after
(only) 200 years!

16
 b) CALCITE NITRIFICATION – there are 2 possible mechanisms:

1) Nitrogen oxides – N2O, NO and NO2 (often generally referred to as NOx) –

contained in the atmosphere can form (in presence of humidity) HNO3.

2) Some types of bacteria use nitrogen oxides or nitrogen-containing

compounds in their metabolism, thereby producing ammonia salts that can
contribute to chemical weathering:

IN BOTH CASES THE ROCK TENDS TO DISINTEGRATE

DUE TO THE VOLUME INCREASE CAUSED BY SALT
CRYSTALLIZATION ( Ca(NO3)2) 17
 c) CALCITE SULFATION

Step 1: Step 2:
2SO2 + O2 2SO3 SO3 + H2O H2SO4

From atmosphere from step 1 and from acid rains

Step 3:
Gypsum: main mineral phase of DARK CRUSTS,

Morphology of
gypsum crystals

inside the dark

crusts

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 Dark crusts

These crusts form in areas exposed to atmospheric pollution, without

relevant washing away by rain water.

Formation mechanism: CALCITE SULFATION

The crust is usually constituted by GYPSUM needle-like crystals matrix, in

which other particles of different origin can be incorporated:
- iron oxides
- quartz crystals
- re-crystallized calcite o re-precipitated calcium carbonate
- atmospheric particulate
- bituminous and carbon-containing particles especially in city
environment: these particles impart the BLACK colour to the crust.

Microscopic investigation (e.g. SEM) reveals a tight bonding of the calcium

sulphate layer to the unaltered portion of stone material lying underneath.

Dark crusts cause THICKNESS INCREASE

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Consequences:

● volume increment of the salt (calcium sulphate) of about 20%

● high affinity to powders (atmospheric carbon-based particulate,

mineral dust), fatty substances, lichens and bacteria the crust
tens to increase its own thickness

● the thermal expansion coefficient of the salt is about 5 times

higher than that of the rock stresses that can induce:
swelling
detachment (flaking, exfoliation…)

In the detachment area of a DARK CRUST, the stone materials

usually appears rough and porous (pitted), and therefore it is more
easily prone to weathering over time.

20
Cathedral of Zamora, Spain: atmospheric
particulate (carbon-based residuum) and lichens
incorporated inside a dark crust on limestone.

Needle-like gypsum crystals disposed

orthogonally to the limestone surface: the crust
thickness is variable, and a clear discontinuity
between crust and limestone can be observed.

Gypsum crystals wedge themselves in

surface micro-cracks, that are thereby
enlarged limestone fragments 21
detachment.
 White coatings

They form where, due to rain water washing away, the dark crusts or other
deposits are continuously removed.

Formation mechanism: CALCITE RE-CRYSTALLIZATION

From a microscopic viewpoint, these crusts are micro-crystalline (or

sometimes amorphous) powder-like CaCO3; coating boundaries are very
irregular and indented.
If the involved areas are very small and localized we may have a
discontinuous coating formed by a wide number of “white points”.

White coating (micro-crystalline and powder-

like CaCO3) on limestone surface with relevant
indentations and pitting the limestone
dissolution is clearly predominant with respect
to the CaCO3 re-precipitation in situ.

22
 Grey areas
● Origin and development:
early or moderate phase of surface weathering that may eventually
ensue in dark crusts
areas involved in the recent detachment of a dark crust where a the early
stages of a new weathering take place (this area is highly reactive and the
dark crust tends to form again)

● Intermediate appearance and structure between

dark crusts and white coatings.

● Apparently, there are NO macroscopic weathering

● The microscopic weathering is less evident than

that in presence of dark crusts.

● Typical features of areas subjected to

moderate washing away

Bust of Saint Marc in Carrara marble (Porta della Carta,

Palazzo Ducale, Venice): dark crusts, white areas where dark
crusts detached dragging portions of marble, grey areas (on 23
the white ones) where dark crusts are slowly reforming.
 Comparison among dark, grey and white areas

THICKNESS CaCO3 CaSO4●nH2O

(µm) (% weight) (gypsum)
(% weight)

DARK CRUST 200-1000 0-8 55-85

GREY AREA 100-200 13-52 25-55

WHITE AREA < 100 64-86 0-6

Apart from the two major constituents (calcite and gypsum), we can also find
carbon-based residual by-products and hydrocarbons (especially in dark
crusts), atmospheric dust and other salts (e.g. calcium nitrate…). 24
Church of San Filippo Neri, Torino (restored in 1997)

Wide and diffused dark crust on the

pronaos before restoration.

Material lack, dark crusts and guano

deposits on Carrara marble

The white and grey

bands and coatings
correspond to the traces
of washing-away waters
(removal of dark crusts
and/or CaCO3 re-
precipitation).

Weathering on Brossasco marble and Gassino stone: lacks 25

and gypsum-based dark crusts.
 Chemical weathering of silicate-based rocks
Case of GRANITE

The mechanism of chemical weathering of granite (main phases: quartz,

feldspar, biotite) is more complex than that of CaCO3-based materials.

QUARTZ it can be considered as unalterable

FELDSPAR can be attacked by water:

orthoclase kaolin (easily removable)

Basification of the water solution
after contact with the mineral reaction slowdown

ACID ENVIRONMENT: the process is accelerated:

26
BIOTITE weathering:

After contact with highly acid waters (pH < 3) the following transformation
occurs:
Vermiculite

Biotite: K(Mg,Fe)AlSiO10(OH)2

New mineral (vermiculite):

(Mg,Al)3(Al,Si)4O10(OH)2·4(H2O)

Vermiculite tends to expand internal stresses, cracking, material

detachments.

Note: vermiculite is commercially used (as aggregates) to produce

27
lightweight concrete.
IMPORTANT: according to a common thinking, granites are estimated to have ultra-
excellent durability: this is NOT true in general, but it must be considered only
partially acceptable!
☺ Use of smooth or flame-treated granite slabs (commonly adopted in
modern buildings) decreases the risk of contact with aggressive agents
(included water)
☺ Rapid increase of the degradation rate at pH < 3 (whereas for carbonatic
rocks, such as limestone and marble, we have rapid increase at pH < 4)
Non-uniform weathering on granite surfaces roughness, de-cohesion
and fragments detachment are particularly favoured by freezing-thaw cycles
Relevant acceleration of weathering processes in humid climates with
frequent rains and low pH.

Cleopatra’s “needle” (Central Park, New York):

it is an obelisk in red granite from Assuan

During only few decades, the rainy climate of

Eastern USA has produced highly superior
degradation in comparison to that occurred during
the past 3000 years in Egypt (dry climate)! 28
 Effect of porosity
A common feature to the majority of stone materials, which strongly can affect their
time-dependent behaviour, is their POROUS STRUCTURE.

POROSITY IS A PROBLEM IN ITSELF ↓ OF MECHANICAL PROPERTIES!

Pores classification (IUPAC nomenclature):
● micropores: < 2 nm
● mesopores: 2-50 nm
● macropores: > 50 nm

POROSITY inside the pores of solids we can find H2O in all its 3 states (ice,
liquid water, gas)
Water can enter the porous body due to CAPILLARY EFFECT: OH¯ groups in the
mineral phases exert attractive forces towards water molecules that thereby enter
the pores (note that capillary pressure ↑ if pores diameter ↓).

Combined effect POROSITY + WATER In general, the process of chemical

weathering (dissolution) are promoted by
the presence of ACIDS (see the processes
of calcite nitrification and sulfation, as well
PROBLEMS ALSO INCREASE! as the biotite weathering) 29
 Crystallization of soluble salts

When saturation conditions occur (i.e., the limit of solubilisation of a salt in

water is surpassed due to T decrease or water evaporation), we assist to the
formation of salt crystals inside pores.

This phenomenon can occur:

● inside the porous network (SUB-FLORESCENCES) exfoliation and

detachment of surface portions

● on the external surface or close to the surface (EFFLORESCENCES)

Note for the efflorescences:

This phenomenon involves THICKNESS INCREASE and CHROMATIC
MODIFICATION on the material surface.

30
 Where do the salts come from?

● From the ground (especially for nitrate- and chloride-containing salts)

● From the deposition of atmospheric aerosols (especially for chloride- and
sulphate-based salts)
● From the stone material itself (e.g.: Ca and Mg sulphates could be
contained in limestones)
● From the materials used for restoration (e.g.: gypsum in Portland cement
formation of sulphates)
● The salts could be the results of chemical degradation processes see
for instance the chemical weathering of carbonatic rocks (nitrification,
sulfation…)
PAY ATTENTION TO CHLORIDES!

The presence of Cl– ions accelerates the iron corrosion of bars or

pins used for stone materials anchorage (e.g. external cladding)

possible detachments of the claddings from the supporting wall! 31

Efflorescence (white coating)

White granite from the Lakes (Verbania): de-cohesion

due to salt crystallization and lack in a pillar of Carlo
Felice Square (Torino)

Large efflorescence and material detachments in several areas

caused by deep sub-florescence
32
 Alveolization
Disintegration action due to high pressure inside the pores that occurred as a
consequence of the increase of the volume of the crystallized salts.

It is conceptually similar to the effect produced by the freezing-thaw cycles.

Fast evaporation (strong air stream) crystallization at relevant depth deep

alveolization (indentation, deep pitting) detachment of large material portions.

Alveoli are often highly interconnected and have

non-uniform size distribution

Alveolization + white efflorescence Corvaja Palace

(Taormina, Sicily)

33
 Biological weathering

Every unwanted change of the properties of a stone material (rock) due to the
action of living organisms.

The involved MECHANISMS of weathering depend on:

type of involved organism
type of substrate
environmental conditions
Types of organisms:

● AUTOTROPHS (or self-feeding) produce complex organic compounds

(such as carbohydrates, fats and proteins) from simple inorganic molecules
using energy from light (by photosynthesis, for the majority of plants and
algae) or inorganic chemical reactions (chemosynthesis, for some algae
and bacteria).

● HETEROTROPHS cannot synthesize organic compounds from inorganic

molecules, but for growing they need pre-synthesized organic compounds
34
by autotrophs (e.g. all animals, fungi and the majority of bacteria).
 Organisms involved in bio-weathering: some details

HETEROTROPHIC BACTERIA can develop and grow only if on the material there
are organic residua (for instance belonging to dead autotrophic microorganisms) or in
consequence of restorative, conservative pr preservative actions (for instance the
use of impregnating polymeric substances etc.).

CHEMOAUTOTROPH BACTERIA exploit the energy derived from the oxidation of

ammonia- or sulphate-derived salts (e.g. NITRIFICANT and SULFOOXIDANT
bacteria).

FUNGI can cause:

● physical weathering: the hyphae (thin filaments constituting the fungus micelium)
can deeply penetrate inside the material rock disintegration.
● chemical weathering: fungi released acids that dissolve the rock due to pH
decrease and can form salts by reacting with metal ions in the stone material.

LICHENS: symbiosis between fungus and alga.

Their growth is very slow; they can develop on the surface in form of crusts or inside
the material penetrating into cavities and cracks. The symbiotic alga can reach up to
25 cm in depth, whereas the fungus hyphae a depth of 2.5 m!
35
MOSS constitutes a class of transition between algae and (superior) plants; they
cause:
● physical weathering: the rhizoids (a sort of small roots) penetrate into micro-
cracks crystals de-cohesion and material disintegration
● chemical weathering: moss exchanges H+ ions (from the water contained in it)
with Ca2+ or Mg2+ from rocks progressive depletion of metal ions from the stone
material.

SUPERIOR PLANTS: weathering caused by roots.

Effects:
● formation of new cracks
● increment and enlargement of pre-existing cracks
● water entrance into these cracks and pits washing away, rock dissolution etc.

ANIMALS: birds are the most dangerous animals for stone materials
Example: pigeons, often diffused in ruins of archaeological sites
Weathering action due to pigeons’ acid dejection (guano)

Particular case: bio-weathering in sea environment by perforating molluscs, whose

acid secretions solubilise and “drill” the rock formation of holes, cavities or
channels with length up to 10-15 cm!
36
Biological green coating (lichens) on a marble sculpture

Crust-like, orange
lichens

Infesting
plants

37
IVY
Deposits of guano on the basis of a column (Vajes
stone, a gneiss from Val Susa) of Saint Christine
Church (Torino); dark crusts, material lacks and
fractures can be also observed.

Relevant deposits of guano on the marble 38

sculptures of the Scalzi Church, Venice
Weathering due to man

Relevant weathering of the basis of the monument

to Italian Knights (Piazza Castello, Torino) in
Simona stone (red sandstone from Val Camonica,
Bergamo): lacks, fractures and graffiti due to
vandalism

39
Fractured slab in Cipollino marble from Tuscany due to wear, pitter pat and
mechanical shocks (corridor paving of Politecnico di Torino)

Cracks in cobblestones of
serpentinite due to ancient
vehicles such as carts and 40
wagons (Valentino Castle, Torino)
NaCl white efflorescence on Simona stone due to the
use of antifreeze salts on the streets

41
 Particular cases: chromatic alteration
Chromatic alteration (“fading”) due to
atmospheric agents in the Portoro
cladding (black limestone from Liguria) at
the shop located Carlo Felice Square, n.
15, Torino.

Columns (Pavonazzetto marble) of the Cathedral of

Sessa Aurunca (Caserta): rust stains and bands
from the metal buckles that supported the entrance 42
iron gate.
 Conservative intervention

a) Preliminary investigations in order to characterize the stone material from

petrographic and mineralogical viewpoints, to assess its origin and to
evaluate its ALTERATION or WEATHERING CONDITION

b) Chemical, physical and mechanical investigations (e.g. optical

microscopy, SEM…) to understand the causes of weathering, with
particular attention devoted to the ENVIRONMENTAL PARAMETERS

c) Conservative actions:
● cleaning
● bonding/pasting/sticking
● grouting (also with plaster)
● consolidation (it might be necessary before cleaning)
● protection (preservative aim against future weathering) for instance
use of polymeric agents forming a thin “skin” on pores surface to
avoid direct contact between stone material and water.

In-Lab simulations: cycles of accelerating ageing (dry-humid, freezing-thaw, hot-

cold) to mimic and forecast the situation of interest 43
real “working” conditions.