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EffectsofAirPollutiononMaterials,IncludingHistoricandCulturalHeritageMonumentsit

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EffectsofAirPollutiononMaterials,IncludingHistoricandCultural
HeritageMonuments
TheInt.CooperativeProgrammeonEffectsonMaterials,includingHistoricandCulturalMonuments(ICPMaterials)startedin1985.
ItwasinitiatedinordertoprovideascientificbasisfornewprotocolsdevelopedwithintheConventiononLongrangeTransboundary
AirPollution.Themainaimistoperformaquantitativeevaluationoftheeffectsofmultipollutantsandclimateparametersonthe
atmosphericcorrosionofmaterials,includingCulturalHeritage.Theprimaryobjectiveistoevaluatedose/responsefunctionsand
trendeffectsandusetheresultsformappingareaswithincreasedriskofcorrosion,andforcalculatingthecostsofdamagecaused
bythedeteriorationofmaterials.HerewepresentthestudyoftwoUNESCOCHsites:theParthenoninAthens(Greece),andthe
buildingfaadesinthecitycentreofParis(France)

StefanDoytchinov,AugustoScrepanti,GiovanniLeggeri
(downloadpdf)
Introduction
Airpollutants,togetherwithclimaticparameters,areofmajorimportanceforthedeteriorationofmanymaterialsusedincultural
monuments.Theyareemittedbyindustrialactivitiesandbythetransportsector.Thesepollutantscreateproblemsonthelocalscale,
buttheyarealsotransportedintheairoverlongdistances.
OneoftheinternationalorganizationsandinstitutionswhichstudytheseeffectsistheUNECEConventionofLongRange
TransboundaryAirPollution(CLRTAP)underwhichoperatetheInternationalCooperativeProgramoneffectsonMaterialsincluding
CulturalMonuments(ICPMaterials),thatstartedin1985.ThisisoneofseveraleffectorientedInternationalCooperative
Programmes(ICPs)dedicatedatstudyingtheharmfuleffectofairpollutiononmaterials.Itwasinitiatedinordertoprovideascientific
basisfornewprotocolsandregulationsdevelopedwithintheConventiononLongrangeTransboundaryAirPollution.
Toreducetheharmfuleffectsofpollutantsonhumanhealthandtheenvironment,theEuropeanDirective1999/30/EChasbeen
issuedrelatingtolimitvaluesforsulphurdioxide,oxidesofnitrogen,particulatematterandleadintheambientair.Theselimitvalues
havebeenestablishedwithreferencetohealthandecosystemeffectsbutnottoeffectonbuildingmaterialsandculturalmonuments.
TheEuropeanculturalheritageisverylargeandcostsbillionsofeurotobemaintained.Itisimportanttounderstandthatsuch
materials,fromwhichtheculturalmonumentsarecreated,aresensitivetopollutionatevenlowerlevelsthanbiologicalsystems.
Thecostsfordeteriorationandsoilingofdifferentmaterialsduetoairpollutionarehugeandthedamagetoculturetargetsseriously
endangerstheculturalheritage.Effectivepolicymakingrequiresenvironmentalimpactassessment,costbenefitanalysisandrisk
management.Allthesetechniquesneedaseriousscientificbasistosupporttheassessmentandthecalculationoftheeffectsof
pollution.
Inthisstudyamethodologyhasbeenappliedtoestimatetherealsurfaceoftheselectedmonumentsandthematerialsfromwhich
theyarecreated,inpercentage.Subsequently,theICPMaterialsdoseresponsefunctionshavebeenusedinordertoevaluatethe
corrosionandsoilingeffectsofairpollutiononthemonuments,andinthenextstudytocalculatethecostsofthedamageduetothe
deteriorationofthematerialsthatthemonumentismadeof.Airpollutiondatafor20092010havebeenused.

TheMethodology[1]
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Themethodologyappliedconsistsofarealinthefieldinventory.Thedimensionsofthemonumentswasidentifiedbydirect
examination,images,photos,drawingsandotherdataavailableinliteratureandfromtheinternetsources.Thedimensionsof
monumentsallowedtocalculatetheirsurfacebyvaluatingthesurfacecoveredbywindows,doors,etc.
Thenatureofthematerialsemployedwasdeterminedbydirectexaminationofthebuildingfaadeorusingtheliteraturesources.
Theproportionsofmaterialswasroughlyevaluatedinpercentage.Thedimensionsofeachmonumentweretakenusingtheliterature
sources,imagesandproportions.Whenthisinformationwasnotavailable,theheightofthebuildingwasestimatedbycountingthe
numberoffloorsandattributingthemanindividualaverageheightof3m.Acontrolofthisarbitraryheightof3mperfloorwas
performedusingalaserbeammeasurementandtheerrordidnotexceed10%(Paris(3)).
Thedeterminationofthelengthofthefaadeswasobtainedbymeasurementsontheavailablecitymaps.Havingheightandlength,
thesurfacewaseasilydeduced.Thesurfaceoftheapertures(windows,doors),classicallyconsideredbyarchitectsequaltohalfof
thetotalsurfaceofthefaades,wasdeducedfromthesurfacematerialsofthemonument.
TheheightandlengthoftheParthenonwereobtainedfromtheofficialtechnicaldocumentsavailableandfromtheliteraturedata.

DoseResponseFunctions
Europe.Itwasestablishedthatthetargetfor2020y.correspondston=2.5.Consideringthebackgroundcorrosionratesduringthe
firstyearofexposuretakenfromtheUN/ECEMappingManual,theestimatedtolerablecorrosionratescalculatedfromEquation(2)
arealmostidenticaltothetolerablelevelsestablishedfrommaintenanceintervals(corrosiondepthbeforeaction/tolerabletime
betweenmaintenance).Itwasdecidedthatthetargetfor2050y.correspondston=2.0.InTable1,thetolerablecorrosionrateforthe
firstyearofexposureforlimestoneisindicatedforthe2020and2050targets.ThetolerablecorrosionratesgiveninTable1arethose
usedforfurtherassessmentoftargetlevelsandarethusconsideredaconservativelowerestimateofthetolerablelevel.Wemay
calculatetheThemostrecentdevelopmentofdoseresponsefunctionsforcorrosioninthenewpollutionsituationinEuropehasbeen
developedincooperationwiththeEUprojectMULTIASSESSbasedondataobtainedintheICPMaterialsmultipollutantexposure
program.Thedegradationoflimestoneisexpressedassurfacerecession(R,m).Thisfunctionincludesarangeofpollutionand
climateparameters(Portlandlimestone):
]RH60+0.054Rain[H+]+0.078[HNO3]Rh60+0.0258PM10(1)

StockatRisk
Weneedauniformapproachforpolicymakersthatmightindicatethemthetargetlevelsofcorrosion.WhentheUN/ECEMapping
Manualisappliedtotolerablelevels,thetolerablecorrosionrate,firstyearexposure(Ktol)canbecalculatedas:
tol

=nxKb(2)

wherenisafactorandKbisthebackgroundcorrosionrate,firstyearexposureforcorrespondingacceptablepollutionconcentrations
fromthetolerablecorrosionrateusingthedoseresponsefunctions.FromthetolerablecorrosionratesindicatedinTable1andthe
realmeasuredorestimatedcorrosionrateswemayestablishifaspecificsitemaybeclassifiedastolerableorexceedence(risk)site.

Tab.1.Tolerablecorrosionratebasedonbackgroundcorrosionratesandthetargetsfor2050(n=2.5)and2020(n=2.0)

Material

Background
corrosion

Tolerable
corrosion
rateper
year

Background
corrosion
depth(BCD)

Factorfor
acceptable
corrosion

3.2m

2020target
(2.5times
BCD)

8.0m
year1

2050target(2.0
timesBCD)

6.4m
year1

Source:[1]

Limestone

Limestone

3.2m

TheParthenonintheAcropolis,Athens

TheParthenon[2](Coordinates:N375815.132,E234334.248)wasincludedintheUNESCOCHlistin1987.TheAcropolis
hill(acroedge,poliscity),socalled"SacredRock"ofAthens,isthemostimportantsiteofthecityandconstitutesoneofthemost
recognizablemonumentsoftheworld.ThemonumentsontheAcropolisreflectthesuccessivephasesofthecity'shistory.Itis3.045
ha.Typesofmainexternalmaterialsusedinpercentage:limestonepentelicmarble(95%),porousstone,sandstone.

Fig.1ThemapoftheAcropoliswiththemonumentsandperiodsofcreation(Orange:Monumentsofthe5thcenturyBCERose:
Monumentsofthe4thcenturyBCEBlue:HellenisticandRomanmonuments)
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[2]

TheParthenonisthemostimportantandcharacteristicmonumentoftheancientGreekcivilizationandstillremainsitsinternational
symbol.ItwasdedicatedtoAthenaParthenos(theVirgin),thepatrongoddessofAthens.Itwasbuiltbetween447and438B.C.and
itssculpturaldecorationwascompletedin432B.C.ThesculpturaldecorationsoftheParthenonareauniquecombinationofthe
Doricmetopesandtriglyphsontheentablature,andtheIonicfriezeonthewallsofthecella.

Fig.2.TheParthenonviewfromNorthEast

[2]
Asindicatedbefore,inordertovaluatequantitativelythelossofmaterialsduetotheairpollutionandtomakeaneconomic
assessment,itisimportanttoknowthesurfacedimensionsofthestudiedmonument.Fromtheliteraturewefoundthegeneral
externalmeasuresofthemonument.Therestwasvaluatedusingtheratiosbetweenknownandunknowndimensionsofthetemple.
Forthisreason,weevaluatedandcalculatedthesurfaceoftheexternal(visible)partoftheParthenon.
ManyoriginalpartsoftheParthenonarelost.AndnowtheTempleiswithoutroofandinternalcell(naos)wheretheGodsstatue
wasoriginallysituated(Fig.2).Fourcolumnsarebroken.ThemostimportantpartsoftheParthenonstillexistingarethecolumns,the
lintel,thetympanum.
Columns:theirsurfaceisnotsmoothbutfluted(Fig.3).Thecolumnsare10mhighandtheirdiameteris1.9m.Thecolumns
arenotcylindersbutthelowerpartisaround30%largerthantheupperone.Inordertofindthecolumncircumferenceweused
asectionofitandthenappliedtheAutoCADsoftware.Thisway,thecircumferenceofacolumnwasfoundtobe7.05m.2.In
thetemplewehave47columns.Fourofthemarebrokenandweconsideredthattheyare50%lost.Thesurfaceofthe
columnsis22=140.8m2.Totalsurfaceofthecolumnsis=2.
Lintel:theshortsidesofitarerelativelyintegral.Theyare29mlongand3.5m.high.TheEastsideis29m(l)x3.5m.(h)=
101.5m2.TheWestsideis29m(l)x3.5m.(h)=101.5m2.TheNorthsideisrelativelyintegralandis69.2m(l)x3.5m(h)=
242.2m2.TheSouthsideisdamagedand29m.arelost,soitis69.229=40.2mx3.5m.=104.7m2.2.
Tympanums(triangles):2.TheNorthsideisverydamaged.Usingtherationsbetweentheintegraleastpartendremaining
piecesfromthe2.Sothetotalsurfaceofthetympanumsis:60.9+15=2.
ThetotalsurfaceoftheParthenonis:2Lintel=549.5mTympanums=75.9m2.TotalvisiblesurfaceoftheParthenonis2.

Fig.3SchemeofaGreektemple

[2]

TheDose/responsefunctionwhichweusedtocalculatetherecessionofthelimestonematerial(seeequation1)for5.60m.Table1
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showsthatthisresultislowerthanthetolerablecorrosionrateperyearforthe2020target,whichis8.0myear1forlimestone.This
resultisveryclosetothetolerablecorrosionrateperyearforthe2050target,whichis6.4myear1.Ontheotherhand,the
calculatedcorrosionratefortheParthenonisalmosttwotimesashighas3.2m).Thismeansthatin20092010thecorrosiondepth
intheParthenonwasalmosttwotimesashighasthebackgroundcorrosionrate,whichisduetoairpollution,butitissteelinthe
rangeoftolerablecorrosionrateforthe2020target.
TheFaadesintheCentreofParis
ThebanksoftheSeine(Coordinates:N485130E21739)havebeenincludedintheUNESCOListoftheWorldCulturalHeritage
(Fig.4)since1991[3].Weshouldconsiderthatmanyimportantmonumentsaresituatedinthisarea.[SeeReport68(1)].Thisstudy
consistsintheevaluationofthestockofmaterialsatriskofdegradation(corrosion,soiling)duetoatmosphericpollution,betweenthe
SullyBridgeontheeasternside,andthePontNeufonthewesternside.ItincludestheIleSaintLouis,theIledelaCiteandtheright
bankoftheSeinefacingthesetwoislands(Fig.4).ThissectoristheverycentreofParis.TheterritoryinscribedontheUNESCOList,
extendstowardsWestasfarastheEiffelTower.Thisstudyincludesroughlyonethirdofthisterritoryandcontainsbuildingsdating
fromtheXVIIandXVIIIcenturies,Haussmannianbuildings(endofXIXcentury),aswellasimportantmonumentslikeNotreDame
andSainteChapelle,datingfromtheMiddleAges.Quaysandbridgeswerenottakenintoaccountinthisevaluation.
Theauthorsmethodologytocalculatethesurfaceofthemonumentconsistedinarealinthefieldinventory,faadebyfaade,
buildingbybuilding,andmonumentbymonument,basedontheParisMapatthescaleof1:2000.Theydeterminatedthenatureof
thematerialsemployedbydirectexaminationofthebuildingfaade(LutetianParisianlimestone,rendering/mortar/plaster,painting,
brick,metal,modernglass)andtheirproportionswereroughlyevaluatedinpercentage.Theyestimatedtheheightofeachbuildingby
countingthenumberoffloorsandattributingthemanindividualaverageheightof3m.Acontrolofthisarbitraryheightof3mper
floorwasperformedusingalaserbeammeasurement:theerrordoesnotexceed10%.Thedeterminationofthelengthofthe
faadeswasobtainedbymeasurementsontheParisMap.Havingheightandlength,thesurfacewaseasilydeduced.Thisentire
surfacewasattributedtotheconstitutingmaterialsaccordingtotheirproportions.Thesurfaceoftheapertures(windows,doors),
classicallyconsideredbyarchitectsequaltohalfofthetotalsurfaceofthefaade,wasnotdeductedbecauseitcompensatesforthe
roughnessofthefaade(sculptures,decoration,balconies,...).Insummary,thetotalcalculatedsurfacewasattributedtothe
constitutingmaterialsandhalfofthissurfacewasarbitrarilyattributedtothemodernglassofthewindows.Onlythestreetfacing,
externalfaadesweretakenintoaccountduetotheirdirectexposuretopollutionfromtrafficandtheinaccessibilityofinteriorprivate
courts.

Fig.4.SatelliteviewofthecentreofParis

[3]
Theauthorsdecidedtomeasurethesurfacesofhistoricalmonumentsdirectlyinthefield,accordingtothesamemethodology
employedforprivatebuildings.IntheIledelaCit,thequantityofhistoricalmonumentsandofficialbuildingsisveryhigh.Onthe
rightbankoftheSeine,threeimportantmonumentsexistandintheIleSaintLouisthereareonlytwohistoricalMonuments.
Intotal,themeasurementofthelengthofeachconstructiononthemapofParis,thecountinginthefieldofthenumberoffloorsand
thecharacterizationandevaluationoftherespectiveproportionsoftheconstitutingmaterialswereperformedonthefaadesof525
buildingsandmonumentsintheCentreofParis,givinganexcellentstatisticalvaluetotheresultspresentedbelow.
ofthe525faadesofbuildingsandmonumentsofthestudiedarea,andthedistributionofthedifferentmaterialsinthesefaades
aregivenherebelowonthebasisofa3mmeanheight.Thesurfaceofmodernglassisarbitrarilyestimatedashalfofthetotal
surfaceofthefaade.ThetwohistoricalmonumentsoftheIleSaintLouishavetheirfaadeentirelyinlimestone,covering768m2,
andtheothersix,intheIledelaCitaccountingfor71,586m2.
2

Withtheseresults,theauthorsdemonstratethatthemainmaterialpresentinthefaadesintheCentreofParisistheLutetian
limestone(roughly76%),followedbypainting(15%)andthenbyrendering(7%).Brick(1%)andmetal(0.02%)playaveryminor
role.Thus,limestonedominatesintheIledelaCiteandontherightbankfacingit,duetothepresenceofmanyimportant
monumentsandHaussmannianbuildings,whereaspaintingandrenderingaremoreimportantintheIleSaintLouis,wherebuildings
aredatingfromtheXVIIandXVIIIcenturies.
TotalParisCentre:525faade=2,lengthof11,203mLimestone:15,933m2(76%)Modernglass(estimated):100,152m2(50%),
others47,247m2(24%).(Monuments):2100%Limestone.
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Thegeographicaldistribution,onagridof100mx100mcells,ofthetotalsurfaceofthefaades,ofthesurfaceinlimestoneandof
thepercentageoflimestoneinthefaades,isgiveninFig.5.Thisconfirmsmoreindetailthatlimestoneismostlyinthewesternpart
ofthestudiedarea.

Fig.5.Geographicaldistributionofthepercentageoflimestoneinthefaadesofbuildingsandmonumentsofthestudiedarea,ona
gridwithcellsof100mx100m(floormeanheight=3m)

[3]

ThemainriskforbuildingsandmonumentsinthecentreofParisisairpollutionduetotraffic,causingthesoilingoffaadesby
depositionofblackcarbonaceousparticles,especiallyinthepartsshelteredfromrain,andthesurfacerecessionofthesefaadesby
erosiondissolutioninthepartsexposedtotherain.TheDose/responsefunctionwhichweusedtocalculatetherecessionofthe
limestonematerial(seeequation1)5.75m.
Table1showsthatthisresultislowerthanthetolerablecorrosionrateperyear,whichis8.0myear1forthelimestone2020target.
Thisresultisveryclosetothetolerablecorrosionrateperyearforthe2050target,whichis6.4myear1.Ontheotherhand,the
calculatedcorrosionratefortheParisCentreisalmosttwotimesashighasthebackgroundcorrosiondepthindicatedinTable1(3.2
m).Thisindicatesthatin20092010thecorrosiondepthintheParisCentrewasalmosttwotimesashighasthebackground
corrosionrate,whichisduetoairpollution,butitissteelintherangeoftolerablecorrosionratefor2020target.

Conclusions
Thepresentstudygivesresultsfromthequantitativecensusofmaterialsinmonumentsbasedonarealinthefieldinventory,andon
directexaminations,applyingmaps,imagesandotherdocumentsattheavailablescales.
Thetypeofmaterialsusedinthemonumentswasdeterminedbydirectexaminationofthebuildingfaade,andtheirproportionswas
roughlyevaluatedinpercentage.Differenttypesoflimestonewereusedintheconstructionofthestudiedmonuments.
Thedimensionsofthemonumentswereidentifiedusingdirectexamination,images,photos,drawingsandotherdocumentsavailable
inliteratureandfromtheinternetsources.Thedimensionsofmonumentsthenallowedtocalculatetheirsurfacebyvaluatingthe
surfacecoveredbywindows,doors,etc.
Aslimestoneisthedominatingmaterial,thedoseresponsefunctionforlimestonewascalculatedinordertodeterminethecorrosion
ofthematerialsusedforconstructingthemonuments.
Usingthepollutiondatafor20092010,theestimatedrecessionrateforbothsitesdoesnotexceedthe2020targetforlimestone
(2.5timesthebackgroundor8.0myear1),butisveryclosetothe2050target(2.0timesthebackgroundor6.5myear1).
However,thecalculatedcorrosionrateforbothsitesisalmosttwotimesashighasthebackgroundcorrosiondepthindicatedinTable
1(3.2m).

References
[1]S.Doytchinov,A.Screpanti,G.Leggeri,C.Varotsos:Pilotstudyoninventoryandconditionofstockofmaterialsatriskat
(UNESCO)CHsites.UNECEICPMaterialsReport68,November2011,preparedbythesubcenterofstockofmaterialsincluding
CHatrisk.
[2]CostasVarotsos,UniversityofAthens,FacultyofPhysics,Dept.ofAppliedPhysics,LaboratoryofUpperAir.BldgPhys5.,
15784Athens,GR,PrivateCommunication.
[3]J.Watt,S.Doytchinov,R.A.Lefvre,A.Ionescu,D.Fuentedela,K.KreislovaandA.Screpanti(2009):Stockatrisk,pp147187,
inTheeffectsofairpollutiononculturalheritage,WattJ,TidbladJ,KuceraVandHamiltonR,Eds.,Springer,NewYork,USA.

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Perinformazioniecontatti:infoEAI@enea.it
StefanDoytchinovENEA,UnitTecnicaTecnologieAmbientali
AugustoScrepantiENEA,UnitTecnicaCaratterizzazione,PrevenzioneeRisanamentoAmbientale
GiovanniLeggeriENEA,UnitTecnicaSviluppodiApplicazionedelleRadiazioni
Energia,AmbienteeInnovazione
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