Influence of different types of heating systems on particulate and gaseous pollutant deposition: the case of churches situated in a cold climate Z. Spolnik 1, A. Worobiec 1, L. Bencs 1,2, L. Samek 3, V. Kontozova 1, R. Van Grieken 1 1 Department of Chemistry, University of Antwerp, Campus Drie Eiken, Universiteitsplein 1, B-2610 Antwerp, Belgium Universiteitsplein 1, B-2610 Antwerp, Belgium 2 Research Institute for Solid State Physics and Optics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest, Hungary Academy of Sciences, P.O. Box 49, H-1525 Budapest, Hungary 3 University of Mining and Metallurgy, Krakow, Poland

The church of Rocca Pietore, Italian Alps.

1. Hot air blowing heating system (HA) 2. Electrical heated pews(El) Investigated heating systems in Rocca Pietore:

Chuch of Szalowa, Poland

Investigated heating systems in Szalowa: Provisory electrical heaters (IR)

1.Energy dispersive X-ray fluorescence analysis (EDXRF) – analysis of bulk samples. 2.Single particle analysis by ultra thin window EPMA – 2. Single particle analysis by ultra thin window EPMA – analysis of size-segregated samples. analysis of size-segregated samples. Gaseous pollutants Particulate pollution  The sampling of NO 2, SO 2 and O 3 gases by diffusion tubes (radiello , Italy). tubes (radiello , Italy).  Analysis – ion chromatography and UV-VIS spectrophotometry spectrophotometry Used analytical methods:

Energy Dispersive XRF (EDXRF)  Analyses of the filters were performed on a Tracor Spectrace 5000 EDXRF instrument.  The measured intensities were converted into elemental concentration by application of the AXIL program code. Low – Z elements analysis by EPMA  JEOL 733 electron probe micro analyser with OXFORD Pentafet EDX detector super atmospheric thin window (U = 10 kV, I = 1 nA)  Liquid-nitrogen-cooled sample stage (T= -193 °C) Classification of particles  Non-hierarchical cluster analysis using Forgy algorithm was applied as statistical method for characterisation of the particles.  Classification of the particles was based on the elemental weight concentrations.

HAOn HAOff ElOn ElOff IROn IROff KCaS Concentration, ng/m 3 x10 -1 Particulate pollution: results of EDXRF

CONCLUSIONS Hot air blowing heating system deteriorates the plastered walls and re-suspends soil dust 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 the concentrations go down very fast However the 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 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 relative abundance (NH 4 ) 2 SO 4 Na-rich Fe-O-rich Ca-O-rich ORG+AlSi ALSI ORG Fine 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 Relative abundance Agglomerates NaCl SiO 2 +org Na-S-O-rich Fe-O-rich Ca-O-rich Ca-rich+org AlSi Organic Results of EPMA – single particle analysis Coarse particle fraction

All the heating systems re-suspend particulate matter brought from outside. According the intensity of the re-suspension, the investigated heating systems can be placed in the following order: We assume that: CONCLUSIONS  Hot-air blowing system Electrical heated pews Electrical heated pews Infra red heaters. Infra red heaters.

Only the hot air blowing heating system Only the hot air blowing heating system could generate pure organic particles. could generate pure organic particles. The application of hot air blowing heating The application of hot air blowing heating system also provoked the deterioration of system also provoked the deterioration of the plastered walls creating an extra internal the plastered walls creating an extra internal source of Ca. source of Ca. The surface of the plastered walls is violated The surface of the plastered walls is violated and deterioration process continues after and deterioration process continues after the changing of the heating system. the changing of the heating system.

Gaseous pollutants (µg/m 3 ) Type of heating system NO 2 SO 2 O3O3 Hot air blowing Inside 10.8  1.1 <DL 0.27  0.03 Outside 5.9  0.2 <DL  4.70 Electrical heated pews Inside 9.4    0.01 Outside 6.3    1.90 NO 2 in Antwerpen museum (inside) µg/m 3

The existence of an internal source of NO 2 The existence of an internal source of NO 2 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. However we assume that the concentrations However we assume that the concentrations of NO 2 found inside the church of Rocca Pietore of NO 2 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. CONCLUSIONS

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