AbstractThis work aims at identifying the reactive zones inside limestone used in monuments exposed to fog. The location of these zones and the depth of the water penetration front is of primary relevance to evaluate the transport of aggressive species and the influence of environmental conditions on alteration mechanisms and kinetics of limestone exposed to the atmosphere. We report herethe results of weathering experiments conducted in a deuterium-enriched environment and the characterization of reactive zones analyzedby NanoSIMS. It was determined that water penetrated several hundred micrometers inside the limestone and that only the first micrometerswere significantly altered

Aurélie-Verney-Carron, 

Chabas, Anne

Duhamel, Rémi

Gonzalez-Cano, Adriana

Loisel, Claudine

Mertz, Jean-Didier

Remusat, Laurent

Rozenbaum, Olivier

Saheb, Mandana

Procedia Earth and Planetary Science

International audienceThis work aims at identifying the reactive zones inside limestone used in monuments exposed to fog. The location of these zones and the depth of the water penetration front is of primary relevance to evaluate the transport of aggressive species and the influence of environmental conditions on alteration mechanisms and kinetics of limestone exposed to the atmosphere. We report here the results of weathering experiments conducted in a deuterium-enriched environment and the characterization of reactive zones analyzed by NanoSIMS. It was determined that water penetrated several hundred micrometers inside the limestone and that only the first micrometers were significantly altered

Verney-Carron, Aurélie

Hal-Diderot

Isotope tracers to investigate reactive zones in stones
from built cultural heritage
Mandana Saheb, Aure´lie Verney-Carron, Laurent Remusat, Re´mi Duhamel,
Adriana Gonzalez-Cano, Jean-Didier Mertz, Claudine Loisel, Anne Chabas,
Olivier Rozenbaum
To cite this version:
Mandana Saheb, Aure´lie Verney-Carron, Laurent Remusat, Re´mi Duhamel, Adriana Gonzalez-
Cano, et al.. Isotope tracers to investigate reactive zones in stones from built cultural heritage.
11th Applied Isotope Geochemistry Conference, Sep 2015, Orle´ans, France. Elsevier, 13, pp.56-
59, 2015, Procedia Earth and Planetary Science. <10.1016/j.proeps.2015.07.013>. <insu-
01241526>
HAL Id: insu-01241526
https://hal-insu.archives-ouvertes.fr/insu-01241526
Submitted on 11 Dec 2015
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 Procedia Earth and Planetary Science  13 ( 2015 )  56 – 59 
1878-5220 © 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license 
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the scientific committee of AIG-11
doi: 10.1016/j.proeps.2015.07.013 
Available online at www.sciencedirect.com
ScienceDirect
11th Applied Isotope Geochemistry Conference, AIG-11 BRGM 
Isotope tracers to investigate reactive zones in stones from built 
cultural heritage  
Mandana Saheba*, Aurélie-Verney-Carrona, Laurent Remusatb, Rémi Duhamelb, Adriana 
Gonzalez-Canob, Jean-Didier Mertzc, Claudine Loiselc, Anne Chabasa, Olivier 
Rozenbaumd  
aLISA, UMR 7583 CNRS UPEC UPD, 61 avenue du Général de Gaulle 
94010 Créteil Cedex, France 
bIMPMC, Sorbonne Universités, UMR CNRS 7590, UPMC, IRD, MNHN, CP52, 57 Rue Cuvier, 75231 Paris Cedex 05, France 
c LRMH, USR 3224, 29 rue de Paris, 77420 Champs-sur-Marne, France  
dISTO, UMR 7327, 1A rue de la Férollerie, 45100 Orléans, France  
Abstract 
This work aims at identifying the reactive zones inside limestone used in monuments exposed to fog. The location of these zones 
and the depth of the water penetration front is of primary relevance to evaluate the transport of aggressive species and the 
influence of environmental conditions on alteration mechanisms and kinetics of limestone exposed to the atmosphere. We report 
here the results of weathering experiments conducted in a deuterium-enriched environment and the characterization of reactive 
zones analyzed by NanoSIMS. It was determined that water penetrated several hundred micrometers inside the limestone and that 
only the first micrometers were significantly altered.  
© 2015 The Authors. Published by Elsevier B.V. 
Peer-review under responsibility of the scientific committee of AIG-11. 
Keywords: limestone, deuterium tracing, water penetration front, alteration mechanisms.  
1. Introduction 
In France, 52% of the patrimonial historical monuments are built out of limestone and the preservation of this 
material is a challenge from a scientific, economic and cultural point of view. The alteration mechanisms need to be 
 
 
* Corresponding author. Tel.: +33-145-171-675 ; fax: +33-145-171-564. 
E-mail address: mandana.saheb@lisa.u-pec.fr 
  e Authors. Published by Elsevi r B.V. This is an open access article under the CC BY-NC-ND license 
(http://creativecommons. rg/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the scientific committee of AIG-11
57 Mandana Saheb et al. /  Procedia Earth and Planetary Science  13 ( 2015 )  56 – 59 
well understood in order to supply proper treatments for their conservation. These processes and associated kinetics 
depend on the mineralogy of the sample and on the environmental conditions.  
We have decided to select one type of limestone, the so called “Saint-Maximin roche fine” widely used for the 
restoration of historical monuments in France, especially in the Paris Basin. This limestone of Lutetian age (45 My) 
is relatively homogeneous as far as chemical composition (on a pristine sample, ca 95% of CaCO3 and 5% of SiO2) 
and physical properties (water transfer properties). The physical and chemical properties of pristine and weathered 
materials from monuments have been presented in other studies [1]. The main alteration phase in weathered samples 
is gypsum (CaSO4, 2H2O) resulting from the reaction between calcite in the stone, water from the environment and 
sulfate from atmospheric SO2 [2]. Moreover, dissolution patterns caused by meteoric water can be observed on 
samples from monuments. In both cases, water action is the main parameter that needs to be investigated.  
To this purpose, we have developed a methodology based on the use of deuterated water. To investigate the 
alteration mechanisms on pristine limestone, a stone block was exposed to controlled environmental conditions, 
aiming at reproducing a succession of dry and wet episodes. During the wet episodes, the use of the deuterium-
enriched synthetic water allowed to locate the water penetration front inside the material and the preferred zone 
where alteration takes place. Locating the reactive zones inside the materials is an important first step to the 
understanding of the alteration mechanisms.   
2.   Methods 
2.1. Weathering experiments 
Limestone block was a cube of 5×5×5 cm3. To simulate an exposition close to natural weathering in the field, 
only one face of the sample was exposed to the environmental conditions, the other being protected by aluminum 
foil. The sample was exposed during 15 weeks to cycles as such: 1 day of fog followed by 6 days of dry atmosphere. 
The frequency of the cycles and the composition of the alteration solution (presented in Table 1) were set based on 
environmental data measured in a Parisian atmosphere.  
     Table 1. Composition of the synthetic water used in weathering experiments 
Species Deuterium pH Na+ NH4+ Ca2+ HCO3- Cl- NO3- SO42- 
Concentration (mol.L-1) 33% 5.4 1,20×10-4 6,75×10-5 5,90×10-5 3,98×10-6 1,29×10-4 4,80×10-5 3,55×10-5 
2.2. Sample characterization and isotopic analyses 
To evaluate the influence of the alteration conditions on the water transfer inside the limestone, cores of 1 cm 
diameter and 5 cm high have been extracted from the stone blocks. Imbibition measurements enabled calculating the 
capillarity absorption coefficient A according to EN 1925 [3]. During the test, the surface in contact with water was 
the one that had been exposed to the environmental conditions. As the capillary properties of the stone are important 
due to the connection between the pores, automatic tests have been performed with a weight measurement every 5 
seconds. 
H isotope, elemental 32S and 16O distributions were imaged on a Cameca NanoSIMS 50 at the MNHN in Paris. 
We acquired quantitative images covering surface areas of 20×20 μm2, divided into 256 by 256 pixels, at a raster 
speed of 1ms/pixel, on transverse sections of the limestone embedded in epoxy. Prior to each analysis, the sample 
area was pre-sputtered with a current of 40 pA for the D analyses and of 650 pA for the 18O and 32S analyses for 
about 5 minutes in order to remove surface contamination and reach sputtering steady state. Due to instrumental 
limitations, H-isotopes were recorded in a first set of images with a current of 3 pA. Then 16O and 32S were acquired 
at the exact same location during a second set of image acquisitions with a current of 50 pA.  
58   Mandana Saheb et al. /  Procedia Earth and Planetary Science  13 ( 2015 )  56 – 59 
3.   Results and discussion 
3.1. Imbibition kinetics 
Fig. 1 a. presents the water absorption kinetics expressed as a weight evolution measurement as a function of the 
square root of the time for weathered and pristine limestone cores. During the first seconds of absorption, the 
kinetics remained the same between the pristine sample and the weathered sample (15 weeks in laboratory). This is 
the result of the initial very high capillary pressure applied at the beginning of the experiment. After this first stage, 
the imbibition kinetics is different between pristine and weathered samples. The decrease of the absorption 
coefficient after several successive cycles simulating dry and wet atmosphere is a well-established phenomenon [4]. 
The evolution could be related to a change of the interfacial tension between the mineral and the water, and/or a 
localized obstruction of the porosity at the surface of the sample linked to a phase precipitation in this zone. 
 
 
 
 
 
 
 
 
 
 
 
 
Fig. 1. (a) Imbibition kinetics measured on pristine and weathered limestone samples, (b) 32S and (c) 16O repartition mapping on the surface of the 
weathered limestone sample. Calcareous zone is on the right side and resin is on the left side of the map. The left side of the calcareous zone has 
been exposed to the fog.  
3.2. Location of the reactive zones 
Fig. 1 b. and c. presents the 16O and 32S mapping obtained using NanoSIMS for a transverse section of the stone 
on a zone located at the surface of the sample in contact with the fog. 16O map allows differentiating the calcareous 
(right side on the map) from the resin zones (left side). At the extreme surface of the sample, a 1μm thick sulfur-
enriched layer is observable. The presence of this layer is probably due to a sulfate-formation process and then 
corresponds to the first alteration stages of the stone. The formation of a sulfate-rich phase at the surface is in good 
agreement with the previous hypothesis of an obstruction of pores located at the surface of the sample that would 
reduce water transfer kinetics. Regarding the composition of the alteration water and the nature of the phases formed 
on samples from monuments, the nature of this phase is probably a calcium sulfate.  
 
3.3. Water front penetration 
The deuterium concentration in the water present in the pores of the limestone is expressed as δD, which is 
calculated following Eq (1).  
 
ߜܦሺΩሻ ൌ ሺሺሺܦȀܪሻ௦௔௠௣௟௘ሻȀሺܦȀܪሻ௦௧௔௡ௗ௔௥ௗሻ െ ͳሻ ൈ ͳͲͲͲ     (1) 
 
On a reference limestone sample that has not been exposed to a deuterated environment, δD is of -390±70‰. Fig. 
2 presents the evolution of δD measured at the surface of grains of the weathered sample as a function of the 
distance to the surface exposed to the deuterated fog. The general trend is a δD decrease from the surface to the 
(a) 
59 Mandana Saheb et al. /  Procedia Earth and Planetary Science  13 ( 2015 )  56 – 59 
inner part of the stone. At 200 μm below the surface, δD is still higher than in a non-deuterated sample, but at 300 
μm below the surface, δD is in the reference range for non-deuterated sample. Consequently, such alteration 
conditions with exposition to cycles of fog and dry episodes only result in limited penetration of the water inside the 
stone. As presented before, it has been possible to identify the presence of a sulfur-rich zone only in the first 
micrometers below the surface. However, modifications are possible to around 300 μm below the surface because 
the water can penetrate to this distance inside the stone. At a macroscopic scale, it influences the water transfer 
inside the stone, as it has been seen with the imbibition tests.   
 
 
 
 
 
 
 
 
 
 
 
 
Fig. 2. Evolution of δD of water in pores as a function of the distance to the surface exposed to the deuterated fog.  
 
4. Conclusion 
It has been possible to simulate in laboratory conditions the cyclic change of fog and dry episodes on limestone 
samples with D-rich water. After 15 weeks of alteration, only the first few micrometers below the surface seem to be 
modified by a visible sulfation process. Moreover, the use of a deuterated solution enabled determining that the 
alterable zone where the water penetrates is of few hundred micrometers below the surface of the sample (under the 
weathering conditions used in laboratory experiments). Besides, the absorption of a thin water layer could facilitate 
the water penetration inside the stone in the case of a heavy-rainy episode. Such events need to be further 
investigated.   
 
Acknowledgements 
The authors would like to thank the French Ministry for Culture and Communication for the financial support. 
The National NanoSIMS Facility at MNHN was funded by CNRS, Région Île de France, Ministère délégué à 
l’Enseignement supérieur et à la Recherche, and MNHN. 
 
References 
1. Saheb M, Mertz JD, Colas E, Rozenbaum O, Chabas A, Michelin A, Verney-Carron A, Sizun JP. Multiscale characterization of limestone used 
on monuments of cultural heritage. MRS Proceedings 2014. 1656. 
2. Sabbioni C. Mechanisms of air pollution damage to stone, The Effects of Air Pollution on the Built Environment, Air Poll. Rev. 2003. 2, 63-
106.  
3. Norme NF EN 1925 Méthodes d'essai pour pierres naturelles - Détermination du coefficient d'absorption d'eau par capillarité 1999.  
4. Beck K, Al-Mukhtar M. Cyclic wetting–drying ageing test and patina formation on tuffeau limestone, Environ Earth Sci, 2014. 71, 2361-2372. 


Isotope tracers to investigate reactive zones in stones from built cultural heritage

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HAL - UPEC / UPEM

Isotope tracers to investigate reactive zones in stonesfrom built cultural heritageMandana Saheb, Aure´lie Verney-Carron, Laurent Remusat, Re´mi Duhamel,Adriana Gonzalez-Cano, Jean-Didier Mertz, Claudine Loisel, Anne Chabas,Olivier RozenbaumTo cite this version:Mandana Saheb, Aure´lie Verney-Carron, Laurent Remusat, Re´mi Duhamel, Adriana Gonzalez-Cano, et al.. Isotope tracers to investigate reactive zones in stones from built cultural heritage.11th Applied Isotope Geochemistry Conference, Sep 2015, Orle´ans, France. Elsevier, 13, pp.56-59, 2015, Procedia Earth and Planetary Science. <10.1016/j.proeps.2015.07.013>. <insu-01241526>HAL Id: insu-01241526https://hal-insu.archives-ouvertes.fr/insu-01241526Submitted on 11 Dec 2015HAL is a multi-disciplinary open accessarchive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come fromteaching and research institutions in France orabroad, or from public or private research centers.L’archive ouverte pluridisciplinaire HAL, estdestine´e au de´poˆt et a` la diffusion de documentsscientifiques de niveau recherche, publie´s ou non,e´manant des e´tablissements d’enseignement et derecherche franc¸ais ou e´trangers, des laboratoirespublics ou prive´s. Procedia Earth and Planetary Science  13 ( 2015 )  56 – 59 1878-5220 © 2015 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).Peer-review under responsibility of the scientific committee of AIG-11doi: 10.1016/j.proeps.2015.07.013 Available online at www.sciencedirect.comScienceDirect11th Applied Isotope Geochemistry Conference, AIG-11 BRGM Isotope tracers to investigate reactive zones in stones from built cultural heritage  Mandana Saheba*, Aurélie-Verney-Carrona, Laurent Remusatb, Rémi Duhamelb, Adriana Gonzalez-Canob, Jean-Didier Mertzc, Claudine Loiselc, Anne Chabasa, Olivier Rozenbaumd  aLISA, UMR 7583 CNRS UPEC UPD, 61 avenue du Général de Gaulle 94010 Créteil Cedex, France bIMPMC, Sorbonne Universités, UMR CNRS 7590, UPMC, IRD, MNHN, CP52, 57 Rue Cuvier, 75231 Paris Cedex 05, France c LRMH, USR 3224, 29 rue de Paris, 77420 Champs-sur-Marne, France  dISTO, UMR 7327, 1A rue de la Férollerie, 45100 Orléans, France  Abstract This work aims at identifying the reactive zones inside limestone used in monuments exposed to fog. The location of these zones and the depth of the water penetration front is of primary relevance to evaluate the transport of aggressive species and the influence of environmental conditions on alteration mechanisms and kinetics of limestone exposed to the atmosphere. We report here the results of weathering experiments conducted in a deuterium-enriched environment and the characterization of reactive zones analyzed by NanoSIMS. It was determined that water penetrated several hundred micrometers inside the limestone and that only the first micrometers were significantly altered.  © 2015 The Authors. Published by Elsevier B.V. Peer-review under responsibility of the scientific committee of AIG-11. Keywords: limestone, deuterium tracing, water penetration front, alteration mechanisms.  1. Introduction In France, 52% of the patrimonial historical monuments are built out of limestone and the preservation of this material is a challenge from a scientific, economic and cultural point of view. The alteration mechanisms need to be   * Corresponding author. Tel.: +33-145-171-675 ; fax: +33-145-171-564. E-mail address: mandana.saheb@lisa.u-pec.fr   e Authors. Published by Elsevi r B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons. rg/licenses/by-nc-nd/4.0/).Peer-review under responsibility of the scientific committee of AIG-1157 Mandana Saheb et al. /  Procedia Earth and Planetary Science  13 ( 2015 )  56 – 59 well understood in order to supply proper treatments for their conservation. These processes and associated kinetics depend on the mineralogy of the sample and on the environmental conditions.  We have decided to select one type of limestone, the so called “Saint-Maximin roche fine” widely used for the restoration of historical monuments in France, especially in the Paris Basin. This limestone of Lutetian age (45 My) is relatively homogeneous as far as chemical composition (on a pristine sample, ca 95% of CaCO3 and 5% of SiO2) and physical properties (water transfer properties). The physical and chemical properties of pristine and weathered materials from monuments have been presented in other studies [1]. The main alteration phase in weathered samples is gypsum (CaSO4, 2H2O) resulting from the reaction between calcite in the stone, water from the environment and sulfate from atmospheric SO2 [2]. Moreover, dissolution patterns caused by meteoric water can be observed on samples from monuments. In both cases, water action is the main parameter that needs to be investigated.  To this purpose, we have developed a methodology based on the use of deuterated water. To investigate the alteration mechanisms on pristine limestone, a stone block was exposed to controlled environmental conditions, aiming at reproducing a succession of dry and wet episodes. During the wet episodes, the use of the deuterium-enriched synthetic water allowed to locate the water penetration front inside the material and the preferred zone where alteration takes place. Locating the reactive zones inside the materials is an important first step to the understanding of the alteration mechanisms.   2.   Methods 2.1. Weathering experiments Limestone block was a cube of 5×5×5 cm3. To simulate an exposition close to natural weathering in the field, only one face of the sample was exposed to the environmental conditions, the other being protected by aluminum foil. The sample was exposed during 15 weeks to cycles as such: 1 day of fog followed by 6 days of dry atmosphere. The frequency of the cycles and the composition of the alteration solution (presented in Table 1) were set based on environmental data measured in a Parisian atmosphere.       Table 1. Composition of the synthetic water used in weathering experiments Species Deuterium pH Na+ NH4+ Ca2+ HCO3- Cl- NO3- SO42- Concentration (mol.L-1) 33% 5.4 1,20×10-4 6,75×10-5 5,90×10-5 3,98×10-6 1,29×10-4 4,80×10-5 3,55×10-5 2.2. Sample characterization and isotopic analyses To evaluate the influence of the alteration conditions on the water transfer inside the limestone, cores of 1 cm diameter and 5 cm high have been extracted from the stone blocks. Imbibition measurements enabled calculating the capillarity absorption coefficient A according to EN 1925 [3]. During the test, the surface in contact with water was the one that had been exposed to the environmental conditions. As the capillary properties of the stone are important due to the connection between the pores, automatic tests have been performed with a weight measurement every 5 seconds. H isotope, elemental 32S and 16O distributions were imaged on a Cameca NanoSIMS 50 at the MNHN in Paris. We acquired quantitative images covering surface areas of 20×20 μm2, divided into 256 by 256 pixels, at a raster speed of 1ms/pixel, on transverse sections of the limestone embedded in epoxy. Prior to each analysis, the sample area was pre-sputtered with a current of 40 pA for the D analyses and of 650 pA for the 18O and 32S analyses for about 5 minutes in order to remove surface contamination and reach sputtering steady state. Due to instrumental limitations, H-isotopes were recorded in a first set of images with a current of 3 pA. Then 16O and 32S were acquired at the exact same location during a second set of image acquisitions with a current of 50 pA.  58   Mandana Saheb et al. /  Procedia Earth and Planetary Science  13 ( 2015 )  56 – 59 3.   Results and discussion 3.1. Imbibition kinetics Fig. 1 a. presents the water absorption kinetics expressed as a weight evolution measurement as a function of the square root of the time for weathered and pristine limestone cores. During the first seconds of absorption, the kinetics remained the same between the pristine sample and the weathered sample (15 weeks in laboratory). This is the result of the initial very high capillary pressure applied at the beginning of the experiment. After this first stage, the imbibition kinetics is different between pristine and weathered samples. The decrease of the absorption coefficient after several successive cycles simulating dry and wet atmosphere is a well-established phenomenon [4]. The evolution could be related to a change of the interfacial tension between the mineral and the water, and/or a localized obstruction of the porosity at the surface of the sample linked to a phase precipitation in this zone.             Fig. 1. (a) Imbibition kinetics measured on pristine and weathered limestone samples, (b) 32S and (c) 16O repartition mapping on the surface of the weathered limestone sample. Calcareous zone is on the right side and resin is on the left side of the map. The left side of the calcareous zone has been exposed to the fog.  3.2. Location of the reactive zones Fig. 1 b. and c. presents the 16O and 32S mapping obtained using NanoSIMS for a transverse section of the stone on a zone located at the surface of the sample in contact with the fog. 16O map allows differentiating the calcareous (right side on the map) from the resin zones (left side). At the extreme surface of the sample, a 1μm thick sulfur-enriched layer is observable. The presence of this layer is probably due to a sulfate-formation process and then corresponds to the first alteration stages of the stone. The formation of a sulfate-rich phase at the surface is in good agreement with the previous hypothesis of an obstruction of pores located at the surface of the sample that would reduce water transfer kinetics. Regarding the composition of the alteration water and the nature of the phases formed on samples from monuments, the nature of this phase is probably a calcium sulfate.   3.3. Water front penetration The deuterium concentration in the water present in the pores of the limestone is expressed as δD, which is calculated following Eq (1).   ߜܦሺΩሻ ൌ ሺሺሺܦȀܪሻ௦௔௠௣௟௘ሻȀሺܦȀܪሻ௦௧௔௡ௗ௔௥ௗሻ െ ͳሻ ൈ ͳͲͲͲ     (1)  On a reference limestone sample that has not been exposed to a deuterated environment, δD is of -390±70‰. Fig. 2 presents the evolution of δD measured at the surface of grains of the weathered sample as a function of the distance to the surface exposed to the deuterated fog. The general trend is a δD decrease from the surface to the (a) 59 Mandana Saheb et al. /  Procedia Earth and Planetary Science  13 ( 2015 )  56 – 59 inner part of the stone. At 200 μm below the surface, δD is still higher than in a non-deuterated sample, but at 300 μm below the surface, δD is in the reference range for non-deuterated sample. Consequently, such alteration conditions with exposition to cycles of fog and dry episodes only result in limited penetration of the water inside the stone. As presented before, it has been possible to identify the presence of a sulfur-rich zone only in the first micrometers below the surface. However, modifications are possible to around 300 μm below the surface because the water can penetrate to this distance inside the stone. At a macroscopic scale, it influences the water transfer inside the stone, as it has been seen with the imbibition tests.               Fig. 2. Evolution of δD of water in pores as a function of the distance to the surface exposed to the deuterated fog.   4. Conclusion It has been possible to simulate in laboratory conditions the cyclic change of fog and dry episodes on limestone samples with D-rich water. After 15 weeks of alteration, only the first few micrometers below the surface seem to be modified by a visible sulfation process. Moreover, the use of a deuterated solution enabled determining that the alterable zone where the water penetrates is of few hundred micrometers below the surface of the sample (under the weathering conditions used in laboratory experiments). Besides, the absorption of a thin water layer could facilitate the water penetration inside the stone in the case of a heavy-rainy episode. Such events need to be further investigated.    Acknowledgements The authors would like to thank the French Ministry for Culture and Communication for the financial support. The National NanoSIMS Facility at MNHN was funded by CNRS, Région Île de France, Ministère délégué à l’Enseignement supérieur et à la Recherche, and MNHN.  References 1. Saheb M, Mertz JD, Colas E, Rozenbaum O, Chabas A, Michelin A, Verney-Carron A, Sizun JP. Multiscale characterization of limestone used on monuments of cultural heritage. MRS Proceedings 2014. 1656. 2. Sabbioni C. Mechanisms of air pollution damage to stone, The Effects of Air Pollution on the Built Environment, Air Poll. Rev. 2003. 2, 63-106.  3. Norme NF EN 1925 Méthodes d'essai pour pierres naturelles - Détermination du coefficient d'absorption d'eau par capillarité 1999.  4. Beck K, Al-Mukhtar M. Cyclic wetting–drying ageing test and patina formation on tuffeau limestone, Environ Earth Sci, 2014. 71, 2361-2372. 

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Isotope Tracers to Investigate Reactive Zones in Stones from Built Cultural Heritage

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