Journal of Cultural Heritage 3 (2002) 8388 www.elsevier.

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Damage on hydraulic mortars: the Venice Arsenal

C. Sabbioni a,*, A. Bonazza a, G. Zappia a,b
b a Institute of Atmospheric Sciences and Climate CNR, Bologna, Italy Dip. di Fisica e di Ingegneria dei Materiali e del Territorio, Univ. Ancona, 60131 Ancona, Italy

Received 20 December 2001; accepted 21 January 2002

Abstract Very few scientic studies have been performed so far on ancient and modern hydraulic mortars. The effects of atmospheric multi-pollutants on hydraulic mortars used in monuments and historic buildings in urban areas, especially those linked to dry and wet carbon and sulphur deposition, remain in need of thorough investigation. In the literature, studies on damage typology identication, composition and origin and relative quantitative data are both scarce and rather poor in quality. While the sulphate source from marine spray deposition and water capillary rising are known, atmospheric sulphur effects on mortars still require elucidation. Ancient and modern hydraulic mortars have been collected from the Arsenal of Venice. The original material characterisation and the evaluation of the surface damage due to atmospheric pollution are presented along with a comparison of the data obtained for the cement and cocciopesto mortars. 2002 ditions scientiques et mdicales Elsevier SAS. All rights reserved.
Keywords: Mortar; Atmospheric deposition; Sulphate; Hydraulic structure

1. Research aim General agreement exists that the atmospheric deposition of primary and secondary multi-pollutants on the surfaces of historic buildings and monuments is the main agent responsible for their deterioration. The most important decay product of the reaction between todays urban atmosphere and building materials is gypsum (CaSO42H2O) due to the wet and dry deposition of SO2 onto the material surface (sulphation process). While the literature reports numerous studies on the environmental behaviour of low porous calcareous stone, such as marbles and limestone [1], there is a conspicuous lack of knowledge/work concerning the impact of atmospheric multi-pollutants on ancient and modern mortars. In fact, because they are composed of an aggregate and a binder, often with different chemical composition, mortars represent heterogeneous systems with high values of porosity and surface roughness, making their decay processes very difficult to study or predict. The few studies performed on mortars have evidenced deterioration phenomena in lime mortars similar to those

encountered in sandstones [2,3]. However, no exhaustive data exist on the environmental behaviour of hydraulic mortars, although they are present in much historic masonry and are still widely used in restoration and modern constructions. In order to ll the gap in knowledge on the durability of hydraulic mortars towards atmospheric multipollutants, samples of plaster and jointing mortars were collected from internal and external masonry in the Venice Arsenal. The aim of the present work is to present the results obtained on the effects of atmospheric deposition on hydraulic mortars and on the difference in the damage mechanisms encountered in the different typologies identied, i.e., cocciopesto and cement mortars.

2. Introduction. Ancient and modern hydraulic mortars in cultural heritage The study of existing mortars in historic structures is an important aspect of building conservation: the choice of their structural elements has varied according to historic period and regional habits. In the past the choice of material was strictly related to the building materials present near the work-areas, transport being both very difficult and expensive. Moreover, depend

* Corresponding author. 2002 ditions scientiques et mdicales Elsevier SAS. All rights reserved. PII: S 1 2 9 6 - 2 0 7 4 ( 0 2 ) 0 1 1 6 3 - 9

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ing on the type of society and the intended use of the nal products, the raw materials were subject to a greater or lesser degree of preliminary processing and preparation. As far as hydraulic mortars are concerned, since ancient times materials of different origins have been added to the lime in order to endow the material with hydraulic properties. The term hydraulic refers to two specic properties: the property of hardening when water is added to the dry binder, and also the capacity to harden under water. These characteristics were achieved as early as the X century BC through the addition of volcanic ash or crushed bricks and tiles (cocciopesto) to the lime binder used in the construction of aqueducts, ports, tanks and other hydraulic works. The Romans in particular fully understood the importance of pozzolan as a raw material in the preparation of hydraulic binders for use in construction exposed to atmospheric weathering. The hydraulic properties are due to the presence in pozzolan of silica (SiO2) and alumina (Al2O3) which, being in an amorphous state and having a high specic surface, react with lime and water to form calcium silicates and aluminate hydrates. The same effect can be attained by using cocciopesto. Hydraulic lime was discovered only in the XVI century. It is obtained by ring marly limestone with a 1015% clay content: the presence of SiO2 and Al2O3 due to the clay decomposition gives rise to the abovementioned hydraulic phases. Hydraulic lime represents the connecting link with Portland cement, the modern hydraulic binder developed in the mid-XIX century. The term cement is used to refer to many different materials, but in the eld of engineering the most common one is ordinary Portland cement (OPC). Usually, OPC is formed by ring marly limestone with a clay content of 2030 % until partial fusion occurs (1450 C). The use of cement spread rapidly in the late-XIX century, eventually assuming its preeminent position among building materials in the XX century [4]. Given the widespread presence of hydraulic mortars, both as original or restoration materials in archaeological and historic monuments, and as normal elements in modern construction, it is of fundamental importance to discover the main damage processes undergone by them, especially those linked to atmospheric pollution, with the aim of identifying a sustainable methodology and a conservation strategy for cultural heritage.

As a rst step, the samples collected were characterised to establish the typology of mortar employing a procedure specically developed for mortar type identication [5]. Optical microscopy observation (OM) of thin sections by a Zeiss Photomicroscope III and X-ray diffraction (XRD) analyses by a Philips PW 1730 were carried out to identify the petrographical and mineralogical components of the material and damage products. Gypsum and carbonates, where present, were quantied by differential and gravimetric thermal analyses (DTA-TGA) with Netzsch STM 429. The morphological features were investigated by scanning electron microscope equipped with an energy dispersive X-ray analyser (SEM-EDX) using a Philips XL 20. In addition, ion chromatography (IC) analysis with a Dionex 4500i were performed to measure the water-soluble anion concentrations in the samples, including SO42. Finally, the non-water-soluble sulphate concentration was evaluated as the difference between the total sulphate fraction, measured by ion chromatography with a specic methodology [6], and the soluble sulphate. The mentioned methodology is based on the complete solubilisation of the sulphates, by treating the sample with a strong cationexchange resin with H+ cycle (Dowex 50 2 with 50100 mesh), and the subsequent quantication of total SO42, including the soluble and non-water-soluble fraction, by ion chromatography. The non-water-soluble SO42 is calculated as follows: SO4
2

non-water-soluble = 2 2 SO4 total SO4 soluble

3.2. Experimental data Already during sampling, it was possible to observe a high degree of surface damage in all the mortars, especially those employed in the external structures (Figs. 1a, b). The mortar-type identication procedure allowed the recognition of the following mortar typologies: lime and cement on both external and interior structures, and cocciopesto, only on external structures. The present work reports only the results of the analyses performed on the hydraulic mortars located in the external masonry, cement and cocciopesto, in order to focus this study on the effects of the same atmospheric environment towards different typologies of hydraulic material. Under optical microscopy the cocciopesto mortars display a carbonate binder with no homogeneous texture and structure, and an aggregate with scarce sorting mainly composed of cocciopesto, the ceramic fragments being easily recognised thanks to their typical brick-red colour, in addition to quartz, carbonate and metamorphic rock fragments, feldspar and sheet silicates (Figs. 2a, b). The aggregate-matrix ratio is about 4050% and the porosity is high, linked previously to the fexural nature with irregular contours. In all the cocciopesto samples, gypsum was

3. Experimental section 3.1. Materials and methodologies Surface layers of plasters and jointing mortars were sampled from the interior and external structures of two buildings (tesone 105 and 106) in the Old Venice Arsenal, which was an area of major commercial and military importance from the origins of Venice through to the period of her maritime supremacy, after which there followed a period of decline.

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Fig. 1. Examples of the sampling area of the external masonry (a, b) of the Old Arsenal.

Fig. 2. Optical micrographs (Nicols X) showing: (a) cocciopesto mortar with clearly dened carbonate matrix, silicatic rock and ceramic fragments; (b) ceramic fragment of the aggregate typical of the cocciopesto mortars; (c) carbonate matrix in a cocciopesto mortar partially transformed into gypsum; and (d) cement mortar showing the alumosilicate matrix with alitic microcrystals.

present as a decay product from the sulphation of the carbonate matrix (Fig. 2c) and carbonate rock fragments. Regarding the cement mortars, OM observations indicate the presence of a hydraulic binder with mainly alitic

microcrystals as typical mineralogical phases (Fig. 2d). In this case the aggregate-matrix ratio ranges between 5065%, and the aggregate has compositional characteristics similar to those described above for the cocciopesto

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Fe, Al)6(S, Al)4O10(OH)8] are also present in some mortars, both cocciopesto and cement (Figs. 3a, b). The DTA/TGA results indicate that gypsum is present in almost all the samples analysed, in quantities varying from 2.25.3%, while carbonates are present in quantities varying from 2050%. The SEM-EDX analyses performed on the sample surfaces show the presence of gypsum crystals with laminar habit, some of which were found to embed carbonaceous particles originating from the atmospheric deposition of particles produced by combustion (Figs. 4a, b). The IC results show in all the hydraulic mortar samples high values of SO42 water-soluble, in concentrations between 10,636 and 31,699 g/g, NO3, ranging between 1519 and 81,301 g/g, and Cl, from 1711 to 129,484 g/g. Smaller quantities for the ion HPO4 (352811 g/g) and water-soluble organic anions were detected: formates (7073391 g/g), acetates (33508871 g/g) and oxalate (5053037 g/g). Finally, the ions NO2, F and Br were found to be present in low concentrations. The concentrations of the water-soluble anions detected in the most representative mortar samples are reported in Table 1. Finally, non-water-soluble sulphate, measured by means of the analytical procedure described above, turned out to be present in all of the hydraulic mortars analysed (Fig. 5).

b Fig. 3. X-ray diffractograms characteristic of a cocciopesto mortar (a) and a cement mortar (b), clearly showing the presence of gypsum.

4. Results The experimental data show that two main typologies of hydraulic mortars have been used in the external structures of the Old Arsenal of Venice; in fact, cocciopesto and cement mortars were found. It is known from the literature that gypsum is the main decay product due to the polluted atmosphere found in calcareous stones, such as marbles and limestones [7], and

mortars, obviously without brick and tile fragments. The cement mortars turn out to be partially transformed into gypsum in the surface layer. The XRD analyses integrate this mineralogical characterisation: along with quartz, calcite, dolomite, feldspar, gypsum and mica as main mineralogical phases identied, halite [NaCl], lizardite [Mg3Si2O5(OH)4] and chlorite [(Mg,

Fig. 4. Scanning electron micrographs showing (a) a carbonaceous particle typical of oil combustion emissions embedded in the gypsum crystals growing as damage products on the surface of the cocciopesto mortar; (b) an alumosilicate particle characteristic of coal combustion emission.

C. Sabbioni et al. / Journal of Cultural Heritage 3 (2002) 8388 Table 1 Concentration of water soluble anions (g/g) present in the most representative hydraulic mortars analysed Samples Cocciopesto 1 Cocciopesto 2 Cocciopesto 3 Cocciopesto 4 Cement 5 Cement 6 Cement 7 SO42 11085 31699 16743 20057 10636 24024 22932 NO3 1709 5146 25152 81301 5271 12443 1519 NO2 191 323 372 415 283 394 399 HPO4 1012 178 35 283 479 2811 84 Cl 1889 6313 129487 11457 1976 8227 1711 F 166 426 14 205 17 180 17 Br 11 64 253 73 32 21 104 CHO2 1050 1820 707 2712 2752 780 3391 C2H3O2 7695 8871 7731 6497 3350 7027 8057 C2O42 417 3037 505 1922 511 523 1662

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lime mortars [8]; the data obtained in the present work show how the damage process triggered off by atmospheric multi-pollutants in hydraulic mortars, both cocciopesto and cement, also lead to gypsum formation. In fact, gypsum is identied as an important mineralogical phase in all of the hydraulic mortars analysed. In the cocciopesto mortars its presence is due to the reaction between the sulphur compounds of atmospheric wet and dry deposition and the carbonate matrix along with the carbonate rock fragments of the aggregate; in the cement mortars the calcium silicoaluminates present in the hydraulic binder and the carbonate fraction of the aggregate undergo sulphation. In some cases, the gypsum damage layer revealed spherical carbonaceous and aluminosilicate particles linked to combustion processes. It has been demonstrated that the carbonaceous particles play a catalytic role in SO2 oxidation on account of their heavy metal content, particularly iron [9]. The IC analyses conrm that gypsum is the main soluble damage product in the mortars analysed, showing that sulphates, together with nitrates and chlorides, are the most abundant anions detected. Finally, the procedure used to determine non-watersoluble sulphates highlights their presence in all of the samples of hydraulic mortars analysed, both cocciopesto and cement mortars. Previous studies on the effects of atmospheric deposition on archaeological, historic and modern European monuments where hydraulic mortars (pozzolan, hydraulic lime and cement) are present, demonstrate that most of the non-water-soluble sulphates can be attributed to ettringite (3CaOAl2O33CaSO432H2O) formation

within the pores of hydraulic mortars, as a result of the reaction between the calcium aluminates of the mortar and the gypsum produced by the sulphation process [4], following the reaction: 3 CaSO42H2O + 3CaOAl2O36H2O + 20H2O 3CaOAl2O33CaSO432H2O The formation of ettringite, a strongly hydrated nonwater-soluble salt, gives rise to a considerable swelling of the mortar mass. A limited amount of this salt, referred to as primary ettringite, always forms in cement mortars due to the small quantity of gypsum (35%) added as a setting regulator during mortar preparation. Primary ettringite, forming during the setting time, does not cause damage, as the uid mortar mixture absorbs the expansion stress produced by its formation. By contrast, when the hydraulic mortar interacts with the sulphates after its hardening, the formation of new ettringite, referred to as secondary ettringite, gives rise to cracks and fractures which seriously damage the material [1012]. In cement mortars this hydrated non-water-soluble salt derives from the reaction between the gypsum originating from the mortar/pollutant (SO2) interaction, on the one hand, and the calcium aluminate hydrates of the binder on the other; in the cocciopesto mortar the gypsum reacts with the calcium aluminate hydrates originating from the reaction between the lime binder and the Al3O2, contained in the ceramic fragments of the aggregate. As can be seen in Fig. 5 the concentration of the total sulphate, water-soluble sulphate and non-water-soluble sulphate in the cocciopesto and cement mortars taken from the Venice Arsenal is similar. In particular, the percentage of non-water-soluble sulphate with respect to the total sulphates is about 13% in both typologies of hydraulic mortars. The presence of non-water-soluble sulphate in amounts higher than 1.73% (corresponding to 35% of gypsum) indicates that a signicant part is formed after the mortar hardening, causing important damage phenomena due mainly to the crystallisation of secondary ettringite.

5. Conclusions
Fig. 5. Mean concentrations of total, soluble and non-water-soluble sulphates (g/g) measured in the cocciopesto and cement mortars sampled in the Venice Arsenal.

The results of this study highlight that among atmospheric multi-pollutants, SO2 is the most aggressive towards

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hydraulic mortars, cocciopesto and cement. The deposition of SO2 onto these two typologies of hydraulic mortars triggers off two important decay mechanisms: a primary damage process, leading to gypsum formation (sulphation), and a secondary process, giving rise to the formation of non-water-soluble sulphates, in particular ettringite. The formation of these two degradation products (gypsum and secondary ettringite) involves a series of physico-chemical processes (expansion, cracking, decomposition of hydration products, etc.) which bring about a loss of cohesion in the material. In addition, the procedure for measuring the non-watersoluble sulphates shows cocciopesto and cement mortars to have similar mean concentrations of these sulphates, proving that the former undergo the same damage process as the latter. In cement mortars the origin of the calcium silicoaluminate hydrates that react with gypsum is in the binder, while in the cocciopesto mortars the source of silica and alumina is in the aggregate. Thus, the effects of SO2 dry and wet deposition on hydraulic mortars is the same, whether the calcium silico-aluminate hydrates come from the binder, as in the case of cement mortars, or from the aggregate-lime binder reaction, as in cocciopesto mortars. The present work demonstrates that the cocciopesto mortars, in the past used throughout the world as a building material and, today, as a restoration material, present the same damage process of other hydraulic mortars, such as pozzolan, hydraulic lime and cement. Further studies are now required to achieve a better understanding of the chemical and microclimatic factors that regulate the non-soluble sulphate formation and its main mineralogical phases.

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Acknowledgements This work is supported by the National Research Council (CNR) within the Programme Progetto Finalizzato Beni Culturali-Subproject 2 as part of the Target Venezia.

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