Alessandra Bonazza Institute of Atmospheric Sciences and Climate (ISAC)
National Research Council
CULTURAL HERITAGE AND TOURISM FOR THE EUROPEAN
FUTURE: ITALIAN APPROACH AND EXPERTISES
Bruxelles, 4 October 2012
Environmental pollution impact on
Cultural Heritage of the European cities
ENVIRONMENT – CULTURAL HERITAGE
-Stone/Masonry Materials:
Marble
Limestone
Sandstone
Bricks
Clay containing mat.
- Wood
- Metals
Iron
Bronze
Copper
Lead
Zinc
- Glass
MATERIALS
- Temperature
- Relative Humidity
- Precipitation
- Wind
- Gas (SO2 , NOx)
- Particles
- Sea salts
- pH precipitation
CLIMATE/POLLUTION
PARAMETERS
INTERACTION
COMBINATION
ACCUMULATION
A. Bonazza, CNR - ISAC, Bologna Bruxelles, 4 October 2012
IMPACT ON CULTURAL HERITAGE - URBAN
•Damage layer and black crust formation
•Chemical dissolution (surface recession)
•Salt crystallisation (decohesion, powdering)
A. Bonazza, CNR - ISAC, Bologna Bruxelles, 4 October 2012
BLACK AREAS
Environment - Cultural Heritage interaction
Marble/limestone in urban areas
WHITE AREAS - Rainwashed areas
- Chemical dissolution
- Material loss
- Rain sheltered areas
- Calcite gypsum (Sulphation
process - SO2)
- Carbonaceous particle deposition
BLACK CRUSTS
SURFACE RECESSION
SULPHATION gypsum (CaSO4•2H2O)
Carbonaceous particles
SOILING AND BLACK CRUSTS
FORMATION
BLACK CRUSTS
A. Bonazza, CNR - ISAC, Bologna Bruxelles, 4 October 2012
1
10
100
1000
10000
100000
1000000
SO4-
-
SO3-
-
NO3-
NO2-
HPO
4-- F-
Cl-
Br-
CHO
2-
C2H
3O2-
C2O
4--
Co
nce
ntr
ati
on
(pp
m)
MILAN
FLORENCE
ROME
VENICE
PARIS
SEVILLE
LONDON
SOLUBLE ANION CONCENTRATION (g/g), IC
SO2 dry deposition Bonazza et al., Atmos. Env. (2005)
SULPHATION PROCESS
Need to expanmd this slide…!.
NOAHs ARK SSPI-CT-2003-501837
Shift in modern urban atmospheres from a SO2
dominated situation to a multipollutant situation
Joakim Langner
CRUSTS : Corrected values (no substrate)
SAMPLES DAMAGE LAYER (%) GYPSUM (%) EC (%) OC (%) OTHERS (%) EC/OC
MILAN 96,08 79,46 1,73 0,70 18,12 2,48
MILAN 95,92 97,35 1,17 0,53 0,96 2,20
MILAN 92,08 76,92 1,70 0,62 20,75 2,75
MILAN 93,92 81,59 1,44 0,20 16,77 7,11
FLORENCE 99,00 64,93 0,46 0,69 33,92 0,68
FLORENCE 83,67 61,69 0,31 0,72 37,28 0,43
FLORENCE 95,58 66,94 0,66 1,11 31,30 0,59
VENICE 87,92 74,83 1,52 0,71 22,94 2,16
VENICE 95,17 56,03 1,89 2,12 39,96 0,89
VENICE 98,67 82,41 0,78 0,67 16,14 1,17
VENICE 94,33 55,98 1,57 2,72 39,73 0,58
ROME 95,83 65,15 1,34 1,62 31,90 0,83
ROME 99,92 65,40 0,93 1,16 32,51 0,80
ROME 93,25 25,80 2,21 3,29 68,70 0,67
PARIS 97,25 70,74 1,84 2,80 24,62 0,66
SEVILLE 91,92 54,00 0,50 3,38 42,11 0,15
SEVILLE 93,42 58,31 0,64 2,37 38,69 0,27
LONDON 88,67 67,81 1,25 2,45 28,49 0,51
LONDON 74,25 57,21 0,93 2,28 39,58 0,41
LONDON 82,50 11,39 0,10 0,81 87,70 0,12
LONDON 51,25 49,66 0,41 3,14 46,79 0,13
LONDON 94,08 64,75 1,01 2,23 32,01 0,45
Gypsum = 80-90%
Modern
A. Bonazza, CNR - ISAC, Bologna Bruxelles, 4 October 2012
TC = CC + EC + OC
Stone
substrate
NCC
Atmospheric deposition
Biological weathering
Surface treatments
Particles emitted by
combustion processes
CARBON IN THE BLACK CRUSTS/DAMAGE LAYERS
Ghedini et al., EST (2006) CARAMEL EVK4-CT-2000-00029
Stationary and mobile sources
CRUSTS European Monuments
(carbonate stone) Substrate
Bonazza et al. Atmos. Env. (2005)
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
FLORENCE ROME PARIS SEVILLE LONDON
OC (%)
EC (%)
OC prevails on
monuments in
European towns
due to
urban traffic
Modern crusts are richer in organic compounds
SITE MONUMENT AGE (years) EC (%) OC (%) EC/OC
MILAN CATHEDRAL 500 1,73 0,70 2,48
MILAN CATHEDRAL 500 1,17 0,53 2,20
MILAN CATHEDRAL 500 1,70 0,62 2,75
VENICE CORNER PALACE 500 1,52 0,71 2,16
VENICE CORNER PALACE 500 0,78 0,67 1,17
ROME VITTORIANO 100 1,34 1,62 0,83
ROME VITTORIANO 100 0,93 1,16 0,80
RAVENNA P. RASPONI 100 0,88 1,67 0,53
FLORENCE S.M. DEL FIORE 50 0,66 1,11 0,59
MILAN CATHEDRAL
OLD-MODERN CRUSTS
VITTORIANO MONUMENT, ROME
A. Bonazza, CNR - ISAC, Bologna Bruxelles, 4 October 2012
Centennial Hall, Poland
Pollution impact on modern
cement built heritage Casa Galleria Vichi (1911),
Florence (Italy)
Reactivity to SO2
0
1000
2000
3000
S t
ot
(µg
/cm
2)
carbonate stones
(mean)
lime mortar pozzolan mortar cement mortar
Vulnerability of building materials is different
depending on chemical composition and porosity
SIMULATION CHAMBER TEST
A
tm
osp
here
Cem
ent
Mo
rtar
SO2
gas SO4=
SO3= SO4
= Catalysts aerosol
Catalysts material
CALCIUM CARBONATE
Gypsum formation on cement
GYPSUM
CALCIUM ALUMINATES
CALCIUM SILICATES
A. Bonazza, CNR - ISAC, Bologna Bruxelles, 4 October 2012
SECONDARY DAMAGE PRODUCTS
3CaO·Al2O3·3CaSO4·31H2O
CaSiO3·CaSO4·CaCO3·15H2O
Gypsum + Calcium silicate
THAUMASITE
Gypsum + Calcium aluminate
ETTRINGITE
Sabbioni et al., Atmos. Env. (2001)
ETTRINGITE
FORMATION
TAUMASITE
FORMATION
10-15 nm
EC Project EDAMM
Laboratory test
Damage occurs in spite of SO2
decreases
BREAKDOWN BY EXPANSION
ETTRINGITE
DISSOLUTION /DECOMPOSITION
St. Maria del Fiore, Florence
1954-1955
Not surveyed
Lucia De Prato
AESTHETIC IMPACT ON SURFACE BUILDINGS
2010
Not surveyed
AESTHETIC IMPACT ON SURFACE BUILDINGS
• Modern urban atmospheres deposit
–less sulfur (phytotoxic)
–more nitrate (nutrient)
–more organic (nutrient)
• Surface yellowing
• Warmer conditions
• Encourage biological damage
(green, grey and black)
Grossi et al., 2006; Bonazza et al., 2007; Grossi et al., 2008, Smith et al., 2010
Technologies and tools to prioritize Assessment
and diagnosis of air pollution impact
on immovable and movable Cultural Heritage
EC Project Teach
ARRIAGA THEATRE, BILBAO
COLOGNE CATHEDRAL
S. MARIA DEL FIORE, FIRENZE
NATIONAL GALLERY, OSLO
NATIONAL MUSEUM, CRACOVIA
Process Most distinctive change
SO2 dry deposition b* (simulation chamber) – yellowish limestone
Blackening (EC!!) L* (field test/in situ analysis) – whitish limestone, marble
Laser irradiation on clean surfaces
a*, b* (laboratory) – reddish limestone, pink granite
Organic consolidant and protective agents application
L* , b* (laboratory) – whitish limestone
Biodeterioration L*, a*, b* (in situ analysis) - calcarenite
Oxidation of trace iron a*, b* - sandstone
Organic pollutants deposition (OC) - yellowing
b* - whitish limestone, marble
Duran-Suarez et al., 1995; Urzì and Realini , 1998; Benavente
et al., 2003; Bonazza et al., 2007, Grossi et al. 2007
To be aware of: surface
roughness (affects L* and C*)
and original material color
Relative colour changes on architectural exemplifying
building stone
mea
n a
*
mea
n
b*
Increase a*: more red Increase b* : more yellow
Florence
Reference
marble
Black crusts /
damage layers
AESTHETIC IMPACT ON SURFACE BUILDINGS
Aerosol monitoring in urban areas
•Gas (SO2, NOx, O3)
•Total suspended particulate (TSP):
(soluble and carbon fraction) Ghedini et al., Atmos. Env. (2011)
Pedestrian area
Traffic
The Florence Baptistery
0,00
20,00
40,00
60,00
80,00
100,00
120,00
TS
P c
on
cen
tra
tio
n (
ug
m-3
)
ND
SD
MR
Monthly mean atmospheric
concentrations of total suspended
particulate at ND (entrance), SD
(exit) and MR during 2003
Non carbonate carbon concentration
(NCC) at ND and SD during 2004
The crucial importance of
performing aerosol monitoring
in the proximity of monuments
is evidenced
by specific campaigns
TRAFFIC
PEDESTRIAN
The unusually severe drought conditions that occurred in summer 2003 may have
reinforced the re-suspended dust contribution from visitors. This phenomenon is
particularly significant in the vicinity of ND, where visitors queued for long periods
prior to entry
FRUITION
ND R2 = 0,9998
SD R2 = 0,3752
0,00
10,00
20,00
30,00
40,00
50,00
60,00
70,00
80,00
90,00
100,00
0 20000 40000 60000 80000 100000
TS
P c
on
cen
tra
tio
n (
ug
m‒3)
Visitors
Winter Autumn
Summer
ND
SD
Ghedini et al., Atmos. Env. (2011)
Visitor impact - Mobility
1. T and RH
2. Solar radiation
3. Wind speed and intensity
4. CO2
5. TSP: soluble and carbon fraction
6. Biological fraction
7. Surface T
Environmental monitoring for the identification of critical
climate and pollution parameters causing deterioration of
building materials
CAMPOSANTO MONUMENTALE, PISA
Monitoring of: Field test on samples
TSP: comparison
Cimitero Monumentale, Pisa
Monitoring, 2007 Battistero, Firenze
Monitoring, 2004
Sito PTS
(μg/m3)
SO4=
(μg/m3)
NO3-
(μg/m3)
Cnc (μg/m
3)
Pisa 47,17 2,31 1,62 0,17
Firenze 52,00 3,99 4,64 17,85
A. Bonazza, CNR - ISAC, Bologna Bruxelles, 4 October 2012
GUIDELINES FOR THE PREVENTIVE CONSERVATION OF
CULTURAL HERITAGE IN EUROPEAN CITIES
-Identify and prioritize climate parameters and pollutants causing
deterioration, depending also on the sensitivity of materials and the
environmental context in which monuments are located.
- Define risks of cultural heritage by adopting continuous environmental
monitoring close to monuments as a valuable tool. Definition of risks allows
heritage managers to single out the priorities for greater investment in
preservation and funding of actions to reduce the cause.
-Promote actions aimed at reducing exposure of cultural heritage to harmful
agents.
-Mitigate the negative causes by regulation at regional and local levels aimed
at the reduction of pollutants, especially in developing urban plans for a
sustainable mobility.
A. Bonazza, CNR - ISAC, Bologna Bruxelles, 4 October 2012
THANKS
Cristina Sabbioni
Adriana Bernardi
Francesca Becherini
Izabela Joanna Ozga
Irene Natali
Chiara Bertolin
Valentina Turci
Paolo Mandrioli
Dario Camuffo
Nadia Ghedini
Giacomo Moriconi
Francesca Tittarelli
Orlando Favoni
Paola De Nuntiis