Influence of different types of Influence of different types of heating systems on particulate and heating systems on particulate and gaseous pollutant deposition: the gaseous pollutant deposition: the

case of churches situated in a cold case of churches situated in a cold climateclimate

Z. SpolnikZ. Spolnik11, A. Worobiec, A. Worobiec11, L. Bencs, L. Bencs1,21,2, L. Samek, L. Samek33, , V. KontozovaV. Kontozova11, R. Van Grieken, R. Van Grieken11

1 1 Department of Chemistry, University of Antwerp, Campus Drie Eiken, Department of Chemistry, University of Antwerp, Campus Drie Eiken, Universiteitsplein 1, B-2610 Antwerp, BelgiumUniversiteitsplein 1, B-2610 Antwerp, Belgium2 2 Research Institute for Solid State Physics and Optics, Hungarian Research Institute for Solid State Physics and Optics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest, HungaryAcademy of Sciences, P.O. Box 49, H-1525 Budapest, Hungary3 3 University of Mining and Metallurgy, Krakow, PolandUniversity of Mining and Metallurgy, Krakow, Poland

The church of Rocca Pietore, Italian Alps.The church of Rocca Pietore, Italian Alps.

1. Hot air blowing 1. Hot air blowing heating system (HA)heating system (HA)

2. Electrical heated pews(El)2. Electrical heated pews(El)

Investigated heating systems in Rocca Pietore: Investigated heating systems in Rocca Pietore:

Chuch of Szalowa, PolandChuch of Szalowa, Poland

Investigated heating systems in Szalowa: Investigated heating systems in Szalowa:

PProvisory electrical heatersrovisory electrical heaters (IR) (IR)

1.1. Energy dispersive X-ray fluorescence analysis Energy dispersive X-ray fluorescence analysis (EDXRF) – analysis of bulk samples. (EDXRF) – analysis of bulk samples.

2.2. Single particle analysis by ultra thin window EPMA – Single particle analysis by ultra thin window EPMA – analysis of size-segregated samples.analysis of size-segregated samples.

Gaseous pollutants Gaseous pollutants

Particulate pollutionParticulate pollution

The sampling of NOThe sampling of NO22, SO, SO22 and O and O33 gases by diffusion gases by diffusion

tubes (radiellotubes (radiello, Italy). , Italy).

Analysis – ion chromatography and UV-VIS Analysis – ion chromatography and UV-VIS spectrophotometryspectrophotometry

Used analytical methods:Used analytical methods:

Energy Dispersive XRF (EDXRF)Energy Dispersive XRF (EDXRF)

AAnalyses of the filters were performed on a Tracor Spectrace 5000 nalyses of the filters were performed on a Tracor Spectrace 5000 EDXRF instrument.EDXRF instrument.

The measured intensities were converted into elemental The measured intensities were converted into elemental concentration by application of the AXIL program code.concentration by application of the AXIL program code.

Low – Z elements analysis by EPMALow – Z elements analysis by EPMA

JEOL 733 electron probe micro analyser with OXFORD Pentafet JEOL 733 electron probe micro analyser with OXFORD Pentafet EDX detector super atmospheric thin window (U = 10 kV, I = 1 nA)EDX detector super atmospheric thin window (U = 10 kV, I = 1 nA)

Liquid-nitrogen-cooled sample stage (T= -193 °C)Liquid-nitrogen-cooled sample stage (T= -193 °C)

Classification of particlesClassification of particles

Non-hierarchical cluster analysis using Forgy algorithm was Non-hierarchical cluster analysis using Forgy algorithm was applied as statistical method for characterisation of the particles.applied as statistical method for characterisation of the particles.

Classification of the particles was based on the elemental weight Classification of the particles was based on the elemental weight concentrations.concentrations.

HAOn HAOff ElOn ElOff IROn IROff

K Ca S0

100

200

300

400

500C

on

cen

trat

ion

, ng

/m3

x10-1

Particulate pollutionParticulate pollution: : results of EDXRFresults of EDXRF

Particulate pollutionParticulate pollution: : results of EDXRFresults of EDXRF

Fe Al Si Cl Zn Ti Pb0

20

40

60

80

100

Co

nce

ntr

atio

n, n

g/m

3

X10-1

HAOn HAOff ElOn ElOff IROn IROff

X10-1

X10-1

X10-1

CONCLUSIONSCONCLUSIONS

Hot air blowing heating system deteriorates Hot air blowing heating system deteriorates the plastered walls and re-suspends soil dust the plastered walls and re-suspends soil dust brought by visitors from outside;brought by visitors from outside;

Electrical heating system re-suspends the Electrical heating system re-suspends the particulate matter brought from outside;particulate matter brought from outside; However However the concentrations go down very fastthe concentrations go down very fast after the heating is switched off.after the heating is switched off.

Infra-red heaters do not influence the re-Infra-red heaters do not influence the re- suspension. suspension.

Results of EPMA – single particle analysisResults of EPMA – single particle analysis

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Hot air (off) Hot air (on) Electrical (off) Electrical (on) IR (off) IR (on)

Type of heating system

rela

tive

ab

un

dan

ce

(NH4)2SO4

Na-rich

Fe-O-rich

Ca-O-rich

ORG+AlSi

ALSI

ORG

Fine particle fractionFine particle fraction

0%

20%

40%

60%

80%

100%

Hot air (off) Hot air (on) Electrical (off) Electrical (on) IR (off) IR (on)

Type of the heating system

Rel

ati

ve

ab

un

dan

ce

Agglomerates

NaCl

SiO2+org

Na-S-O-rich

Fe-O-rich

Ca-O-rich

Ca-rich+org

AlSi

Organic

Results of EPMA – single particle analysisResults of EPMA – single particle analysis

Coarse particle fractionCoarse particle fraction

AAll the heating systems re-suspend particulate ll the heating systems re-suspend particulate matter matter bbroughtrought from outside. from outside.

According tAccording the intensity of the re-suspension, he intensity of the re-suspension, the investigated heating systems can be the investigated heating systems can be placed in the following orderplaced in the following order::

We assume that:We assume that:

CONCLUSIONSCONCLUSIONS

HHot-air blowing systemot-air blowing system

EElectrical heated pewslectrical heated pews

IInfra red heaters.nfra red heaters.

OOnly nly the the hot air blowing heating systemhot air blowing heating system could could generate pure organic particles. generate pure organic particles.

The application The application of hot air blowing of hot air blowing heating heating system also provoked the deterioration of system also provoked the deterioration of the plastered walls creatithe plastered walls creating an ng an extra internal extra internal source of Ca.source of Ca.

• TThe surface of the plastered walls is violated he surface of the plastered walls is violated andand deterioration process deterioration process ccontinuesontinues after after thethe changing ofchanging of the heating system. the heating system.

Gaseous pollutants (µg/mGaseous pollutants (µg/m33))

Type of heating system

NO2 SO2 O3

Hot air

blowing

Inside 10.8 1.1 <DL 0.27 0.03

Outside 5.9 0.2 <DL 11.80 4.70

Electrical

heated pews

Inside 9.4 0.6 0.11 0.09 1.18 0.01

Outside 6.3 1.5 1.40 0.50 18.40 1.90

NONO22 in Antwerpen museum (inside) 23-34 µg/m in Antwerpen museum (inside) 23-34 µg/m33

The existence of an internal source of NOThe existence of an internal source of NO22

caused by the combustion of diesel oil in the caused by the combustion of diesel oil in the fuel-chamber and/or burning candle is assumed. fuel-chamber and/or burning candle is assumed.

HoweverHowever we assume that the concentrations we assume that the concentrations of NOof NO22 found inside the church of Rocca Pietore found inside the church of Rocca Pietore

are not dangerous for the art works stored there.are not dangerous for the art works stored there.

CONCLUSIONSCONCLUSIONS

THANK YOU FOR YOUR ATTENTION!THANK YOU FOR YOUR ATTENTION!