Environmental pollution impact on Cultural Heritage of the ...

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)


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


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


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



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


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


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


• 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


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


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.


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

Environmental pollution impact on Cultural Heritage of the ...

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