The effect of air pollution on stone decay: the decay of the Drachenfels trachyte in industrial, urban, and rural environments—a case study of the Cologne, Altenberg and Xanten cathedrals

Severe stone deterioration is evident at the Cologne cathedral. In particular, the “Drachenfels” trachyte, which was the building material of the medieval construction period, shows significant structural deterioration as well as massive formation of gypsum crusts. The present article investigates crust formation on limestone, sandstone, and volcanic rock from the Cologne cathedral as well as from the Xanten and Altenberg cathedrals. These three buildings, showing varying degrees of deterioration, are located in different areas and exposed to varying industrial, urban, and rural pollution. Thin laminar and black framboidal crusts form on calcareous as well as silicate stone. The lack of a significant intrinsic calcium and sulfur source for the formation of the gypsum crusts on the Drachenfels trachyte indicates major extrinsic environmental impact: a sufficient offer of SO _x from pollutant fluxes as well as external calcium sources (e.g., pollution, mortars, neighboring calcite stones). Chemical analyses reveal strong gypsum enrichment within the crusts as well as higher concentrations of lead and other pollutants (arsenic, antimony, bismuth, tin, etc.), which generally can be linked to traffic and industry. The formation of weathering crusts in an industrial environment is clearly distinguishable from that in rural areas. Scanning electron microscopy observations confirm that the total amount of pollution is less at the Altenberg cathedral than at the Cologne and Xanten cathedrals. XRF analyses show that the formation of gypsum occurs in lower amounts at Altenberg. This correlates well with the measured SO₂ content and the intensity of the decay at the different locations. Furthermore, the different types of crusts, e.g., framboidal and laminar, can be differentiated and assigned to the different locations. The black weathering crusts on the silicate Drachenfels trachyte contribute to the degradation of the historic building material. They enhance mechanical moisture-related deterioration processes and the decay by chemical corrosion of rock-forming minerals. Although SO₂ concentrations in air have shown a strong decrease over the past 30 years, degradation in connection with weathering crusts is still observed. This indicates that not only contemporary or recent emissions, but also past pollutant concentrations have to be considered.     

Weathering behaviour and construction suitability of dimension stones from the Drei Gleichen area (Thuringia, Germany)

The construction suitability of a dimension stone depends on its weathering properties along with the petrology and the petrophysical properties. The aim of this study was to evaluate the suitability of the dimension stones from the “Drei Gleichen” area for construction and replacement purposes. In total, six sandstones (Ingersleben, Wachsenburg, Hindfelden, Seeberg, Röhnberg, Gleichenberg; Upper Triassic) as well as two carbonates (Wachsenburg sinter; Quaternary, Wandersleben dolomite; Middle Triassic) were analysed. The results from our laboratory and on-site studies of the dimension stones show that rocks from the same stratigraphic layer, like the sandstones from the upper Triassic, can show major differences in their petrophysical and weathering properties. These differences are attributed to their different diagenesis, resulting, e.g. in varying pore space, water balance and strength properties. The pore size distribution can be divided into four different groups based on their occurring maxima and micropore content. The determined water balance properties as well as moisture expansion and salt attack depend on these groups. Next to this, the mineralogical composition significantly influences the weathering resistance. Sandstones with a high content of altered lithoclasts show a high amount of moisture expansion, low strength and, in consequence, a low weathering resistance against salt attack. Based on the results of the present study, an evaluation of construction suitability could be accomplished. From the analysed sandstones, only the Seebergen sandstone is suitable for construction purposes due to its good availability, good strength properties (high compressive and tensile strength, low softening degree) as well as a low porosity. Furthermore, the Wachsenburg sandstone also shows good petrophysical and petrological properties, but exploitable deposits are too sparse to be of commercial interest. From the carbonates, the Wachsenburg sinter shows very suitable rock parameters, but only sparse outcrops occur, which are not appropriate for mining.     

Physical weathering of building stones induced by freeze–thaw action: a laboratory long-term study

Damages to natural building stones induced by the action of frost are considered to be of great importance. Commonly, the frost resistance of building stones is checked by standardised freeze–thaw tests before using. Corresponding tests normally involve 30–50 freeze–thaw action cycles. In order to verify the significance of such measurements, we performed long-term tests on four selected rocks over 1,400 freeze–thaw action cycles. Additionally, numerous petrophysical parameters were analysed to compare the behaviour of rocks in the weathering tests according to the current explanatory models of stress formation by growing ice crystals in the pore space. The long-term tests yield more information about the real frost sensibility of the rocks. A clear deterioration cannot be determined in most cases until 50 weathering cycles have been completed. In the freeze–thaw tests, the samples are also stressed by changing temperature and moisture, indicating that different decay mechanisms can interfere with each other. Thus, thermohygric and moisture expansion are important damage processes.     

Weathering of volcanic tuff rocks caused by moisture expansion

Moisture expansion in natural building stones is considered one of the most important factors affecting their weathering and deterioration. The processes that may be responsible for the expansion under determinate relative humidity (hygric dilatation) and water-saturated conditions (hydric dilatation) are generally attributed to the presence of swellable clay minerals. In contrast to this assumption, our investigations show that moisture expansion also takes place in volcanic tuff building stones almost free from clay minerals. To provide a deeper understanding of the processes, swelling and deterioration were performed on 14 volcanic tuffs used as important building stones of different ages, compositions and weathering stages from Mexico, Germany and Hungary. The investigations undertaken include extensive chemical, petrophysical and fabric analyses. The samples show a wide range of effective porosity, microporosity, capillary water absorption, moisture expansion, and CEC values. High moisture expansion does not seem to depend on clay mineral content alone. We also observed that there is no significant effect on dilatation if clay minerals are present but only form a thin coat on the outer shell of bigger pores. Moreover, we identified a correlation between microporosity, average pore radius and moisture expansion. The investigations highlight the fact that moisture expansion cannot only be attributed to swellable clay minerals, and suggest that the presence and accumulation of micropores and their average radius and distribution play an important role for non-clay associated swelling intensity, which can most probably be attributed to the disjoining pressure.     

Natural building stones of Mexico–Tenochtitlán: their use, weathering and rock properties at the Templo Mayor, Palace Heras Soto and the Metropolitan Cathedral

In the Aztec period and in colonial times different natural stones originating in the Valley of Mexico were used for building construction. Stone weathering was investigated onsite at various historical buildings within the old quarter of Mexico City. In this study, different aspects of weathering and deterioration at three significant historical buildings will be presented, the Aztec excavation site Templo Mayor, the Metropolitan Cathedral, and the colonial palace of the dukes of Heras Soto. Petrophysical properties of the main building stones of these structures were investigated like density, porosity, pore radii distribution, water uptake rate and coefficient, thermal and hygric expansion, and the mechanical properties of uniaxial compressive strength. A relationship between single critical property values, according to anisotropy fabric characteristics, and specific weathering forms could be deduced.     

The combined effect of moisture and temperature on the anomalous expansion behaviour of marble

Three calcitic marble types often used as cladding material and different in lattice preferred orientation (texture), grain shape preferred orientation, grain size distribution and grain interlocking are investigated to study the combined effect of thermal cycles (day-night) and moisture on the decay of marble, particularly on the bowing phenomenon. Repetitive heating-cooling under dry conditions leads to considerable inelastic residual strain only in the first thermal cycle. The residual strain continuously increases again if water is present, whereby the moisture content after a thermal cycle has a certain impact on the decay rate. The water-enhanced thermal dilatation strongly correlates with the deterioration rate obtained from the laboratory bow test. All applied approaches reveal that the texture in combination with the grain shape preferred orientation control the intensity and anisotropy of marble deterioration, thus, the cutting direction of facade panels has to be considered in terms of durability. On-site analysis from building facades confirm the laboratory results such as the bowing tendency of different marbles, directional dependence, relevance of moisture content during cyclical heating and the loss of strength due to environmental impact.Special Issue: Stone decay hazards     

Thermal expansion of granitoids

The thermal rock properties are particularly important for natural stones whenever a temperature change may occur, which becomes particularly important when different materials are combined on any architectural structure. The thermal expansion of a rock is dependent on the coefficients of the expansion of the individual rock-forming minerals and the rock fabric. A systematic study on 65 different stones, mostly granitoids and others magmatic rocks, most of them are often used as dimensional building stones, was performed. Temperature and moisture are very important parameters in the natural environment. Therefore, the thermal expansion, and in addition the thermohygric expansion on selected examples, was measured. The data were also discussed considering the effect of the mineralogy and the temperature. A modeling approach was introduced to show how the mineralogy and the related single crystal properties affect the thermal properties and how good a simple calculation can help to characterize the measured thermal expansion of a rock. The directional dependence of the thermal expansion was also discussed and explained based on detailed rock fabric measurements. In this study, the bowing of granitoid samples was tested and compared with bowing phenomena of granitoid facade panels. The slabs were cut in different directions and were studied under different conditions of temperatures and water saturation. It could be clearly documented that the temperature and the moisture have a control on the bowing behavior. The implication of our data is that thermal expansion depends greatly on wetting and drying, i.e., the thermal cracking is characterized by the residual strain observed after cooling to room temperature. The sensitivity to the thermal cracking has a significant control on the application in architectural constructions.     

A methodology for locating the original quarries used for constructing historical buildings: application to Málaga Cathedral, Spain

It is often necessary to locate the original quarry which supplied the stone for a particular historical building. This stones could be used for future restoration work and for testing in the laboratory (artificial aging tests, physical properties determination, control of the efficacy of conservation treatments, etc.). Generally, reviewing historical documentation gives information about the geographical setting of quarries and location of the stones in the monument, but this information needs to be proved by field and laboratory studies. The comparative study of stone from quarries and monuments should basically include the following: (1) mineralogical and petrographical studies; (2) the chemical analysis of major, minor and trace elements; (3)stable isotopes determinations; (4) physical properties of quarry materials and unweathered building stone (water absorption, ultrasound transmission velocity, porosity and porous system, density, bulk density, compressive strength, etc.). This methodology was applied to Málaga Cathedral stones represented in the main façade, towers, and the western zone of the terrace, which, according to historical literature, came from Almayate (Miocene–Pliocene limestones) and Cerro Coronado (Permotriassic sandstone) in Málaga. The conclusion of the comparative study carried out on quarries and building stones was consistent with the information available from the historical documentation.     

Moisture expansion as a deterioration factor for sandstone used in buildings

The expansion processes that develop in building stones upon changes of moisture content may be an important contributing factor for their deteriorations. Until recently, few data could be found in the literature concerning this parameter and weathering processes. Moreover, the processes that may be responsible for the moisture related expansion of natural building stones are not yet completely understood. To further elucidate this process, extensive mineralogical, petrophysical and fabric investigations were performed on eight German sandstones in order to obtain more information regarding the weathering process and its dependence on the rock fabric. The analysed sandstones show a wide range of pore size distributions and porosities. A positive correlation with the fabric and the pore space can be found for all studied petrophysical parameters. The intensity of the expansion and related swelling pressure cannot be attributed only to the swelling of clay minerals. The investigations suggest that the micropores and the resulting disjoining pressure during wet/dry cycles also play an important role. The results obtained suggest that the mechanism is related to the presence of liquid water within the porous material.     

Black dimensional stones: geology, technical properties and deposit characterization of the dolerites from Uruguay

Dimensional stones with a black color occupy a prominent place on the international market. Uruguayan dolerite dikes of andesitic and andesitic–basaltic composition are mined for commercial blocks of black dimensional stones. A total of 16 dikes of both compositions were studied and samples collected for geochemical and petrographical analysis. Color measurements were performed on different black dimensional stones in order to compare them with the Uruguayan dolerites. Samples of the two commercial varieties (Absolute Black and Moderate Black) were obtained for petrophysical analysis (e.g. density, porosity, uniaxial compressive strength, tensile strength, etc.). Detailed structural analyses were performed in several quarries. Geochemistry and petrography determines the intensity of the black color. The Uruguayan dolerite Absolute Black is the darkest black dimensional stone analyzed in this study. The petrophysical properties of Uruguayan dolerites make them one of the highest quality black dimensional stones. Structural analyses show that five joint sets have been recognized: two sub-vertical joints, one horizontal and two diagonal. These joint sets are one of the most important factors that control the deposits, since they control the block size distribution and the amount of waste material.     

Petrophysical and mechanical properties of Euganean trachyte and implications for dimension stone decay and durability performance

Euganean trachyte is a subvolcanic porphyritic rock extracted in northern Italy with an age-old tradition of use as dimension stone, historically linked, in particular, to the fervent building activity brought by the Roman Empire and, later on, the Republic of Venice Serenissima. The results of a comprehensive petrophysical and mechanical characterization of Euganean trachyte from the most representative quarries are discussed here, involving the following properties: density, porosity, water absorption, capillary water uptake, hygroscopic water adsorption, hydric/hygric dilatation, water vapor diffusion, thermal expansion, and resistance to salt attack and abrasion. The different trachyte varieties, although belonging to the same quarry basin, exhibit a relatively wide array of technical performances, which are strongly dependent on pore volume, size, size distribution, shape, and degree of interconnection, controlling modes and rates of water transport and retention. Therefore, indications are provided for evaluating durability performance of the stone, with stress on water-driven weathering. Complementary information is finally given on the possible criteria followed in the antiquity for properly selecting the trachyte quarries to be exploited, and by a comparison with the properties of the most important trachytes extracted in Europe.     

Damage phenomenon and petrophysical properties of sandstones at the Phnom Bakheng Temple (Angkor,Cambodia): first investigations and possible conservation measures

Sandstones, clay in the form of bricks and laterite are the building materials used by the Khmer to construct the imposing and magnificent temples in Southeast Asia. Many of these monuments suffer from fracturing, sanding, contour scaling, crust formation and salt weathering. The affinity to weathering is closely connected to the type of material. Two sandstone types classified as feldspathic arenite and quartz arenite of Angkor as well as two arkosic sandstones from Thailand are described and investigated in this study. Important petrophysical properties determined for the different sandstones consist of hydric expansion, thermal expansion, pore radii distribution and ultrasonic velocity. Different investigations such as capillary water uptake, surface hardness, hygroscopic water sorption, and salt resistance tests were undertaken in the laboratory to characterize the various rock types. Observations and quantified damage mapping were done onsite at the Phnom Bakheng Temple. Contour scaling in the form of weathering crusts is one of the main deterioration features observable at the Angkor monuments. Comparisons are made between the building stone, the crust material from the Phnom Bakheng Temple and fresh stone material used for restoration. Significant differences in hydric and especially in thermal expansion of the crust and sandstone have been determined. The results seem to indicate that extensional processes occur, which can be considered a force for detachment (i.e., contour scaling, flaking). In an experimental trial, the hydric and thermal expansion of the weathering crust and the building stone was significantly reduced by using a weak acid for the crust and a swelling inhibitor for the original building stone.     

Marble bowing: comparative studies of three different public building facades

The veneer cladding of the Oeconomicum (OEC, Göttingen), the State Theatre of Darmstadt (STD, Darmstadt) and of the State and University Library (SUB, Göttingen) is characterised by pronounced bowing after a short time of exposure. Direct comparison of bowing data related to measurements from 2000 to 2003 at the SUB clearly show that the amplitude in bowing had significantly increased. The bowing is different in intensity and orientation (concave, convex). The cladding material (Peccia marble, Rosa Estremoz marble and Carrara marble) are different in lattice preferred orientation, grain size distribution and grain interlocking. Depending on the bowing, panels may show cracks mostly initiated at the dowels. The percentage of visible cracks and breakouts increases with the amplitude of bowing except for the STD. Repetitive heating–cooling under dry conditions leads to considerable inelastic residual strain only after the first or second thermal cycle. The residual strain continuously increases again if water is present, whereby the moisture content after a thermal cycle has a certain impact on the decay rate. The water-enhanced thermal dilatation strongly correlates with the deterioration rate obtained from the laboratory bow test. Detailed petrophysical investigations provide evidence that with increasing bowing a decrease of mechanical properties (flexural strength or breaking load at dowel hole) occur. Marble degradation is also connected with the increase in porosity and a general shift of the maximum pore radii to larger pore sizes. On-site damage analyses were combined with laboratory tests of the bowing potential to constrain factors that may influence the risk failure. The experimental bowing data clearly demonstrate that after 40 heating cycles combined with the effect of moisture a certain impact on the decay rate is observed. In the case of demounted panels the bowing tests show that already strongly deformed panels from the building exhibit a lower bowing potential than those with lower amplitudes of bowing. This is not the general case for all marble types. Finally, the artificial bowing causes a significant reduction of the flexural strength and the breaking load at the dowel hole. The strength loss of the experimentally aged claddings combined with on-site damage analyses led to conclusions concerning risk assessment and the predicted lifetime of the investigated marble claddings.     

三峡库区巫峡段典型岩体劣化特征研究

三峡工程形成了在高程145~175 m之间的周期性水位波动,促使库区灰岩岸坡劣化损伤加剧,稳定性急剧衰减。其中巫峡段灰岩岸坡受库水长期的物理化学作用,宏观劣化现象最为明显,局部顺层岸坡底部受侵蚀劣化脱空,岩层出露,存在潜在的滑移-拉裂破坏。文章借助三维激光扫描点云技术对岩体表层宏-细观劣化进行了定量化观测,发现岩体劣化主要沿着泥质填充条带等薄弱结构面进行,现场“刀砍纹”状溶蚀沟槽的差异劣化与白云石和方解石抗溶蚀性能密切相关。室内干湿循环劣化试验进一步表明:三叠系大冶组(T1d)泥质条带灰岩的劣化速率明显高于三叠系嘉陵江组(T1j)白云质灰岩,这与两种岩性的矿物成分及孔隙微观结构组成相关,且随着循环周期增加,两种岩样的物理力学性质呈现出不同程度的衰减;基于核衰变劣化控制式进行回归,R2高达0.861 9~0.999 3。引入劣化常数λ、半衰期T1/2对两种岩性劣化特征进行描述,发现同一岩性不同物理参数对应的劣化常数λ、半衰期T1/2不同,呈现“簇状”分布,与室内试验数据表现一致;运用劣化控制式时要考虑现场岩体由于各种结构面的存在,岩体会加速劣化,需要对劣化控制方程和力学强度进行相应折减。文章结合现场宏-细观劣化现象以及室内干湿循环,构建了物理意义明确的基于核衰变的劣化控制方程,为类似灰岩岸坡劣化评估预测与稳定性分析提供参考。     

Decay mechanism of indoor porous opuka stone: a case study from the main altar located in the St. Vitus Cathedral,Prague (Czech Republic)

A carving of the indoor main altar of St. Vitus Cathedral in Prague (Czech Republic) is made of the opuka stone—a clayey–calcareous silicite—which now exhibits the development of decay phenomena such as the formation of salt-laden case-hardened subsurface layer (approx. 150 mm thick), with detachment of the case-hardened layer manifested by blistering and/or flaking. Formation of this gypsum-rich layer is linked to the reaction of components (SO₂) from polluted air (both outdoor and indoor) and from the rock itself (calcium ion from calcite). Development of brittle damage in the subsurface layer and underlying stone is interpreted based on the results from previous environmental monitoring in the Cathedral’s interior, which indicated highly fluctuating temperature and humidity, resulting in a hygrothermal stress in the material described by the “double-layer sandwich” model. The sensitivity of the studied stone to the above-mentioned processes is evidenced by its microstructural properties, specifically parameters of the pore spaces which indicate an extremely high susceptibility to damage by the actions of freezing water and/or salt crystallisation.     

Granitic dimensional stones in Uruguay: evaluation and assessment of potential resources

In Uruguay commercial granite varieties comprise mafic rocks, granitoids, and syenitoids. There is a long tradition in Uruguay, as well as worldwide, of using dimensional stones in architecture and art, specially granitic ones. Some of the present applications of these dimensional stones are as façade cladding, countertops, and outdoor and indoor floor slabs. The color spectrum of the Uruguayan granitic dimensional stones varies from black to light gray, covering a wide variety of red and pink and minor greenish-gray. The décor of these granitic dimensional stones is mainly determined by their fabric, fundamentally the grain size and the color distribution between the different minerals that compose the rocks. In the present research the most important commercial granites were sampled to analyze their petrography and petrophysical properties. A detailed structural analysis has been performed in several deposits, as well as the application of the software 3D Block Expert for modeling the possible raw block size distribution. Other factors controlling the mining viability of the deposits were also studied (e.g., homogeneity/heterogeneity of color and décor) and the possible reserves were calculated.     

Moisture expansion associated to secondary porosity: an example of the Loseros Tuff of Guanajuato, Mexico

The old mining city of Guanajuato in middle Mexico preserves one of the most important historical legacies in colonial buildings, the UNESCO declared the city World Heritage Site in 1988. Practically all the colonial constructions were built with natural stones from the neighbourhood, of which stands a greenish to reddish vulcanite, called Loseros Tuff. Although the Loseros Tuff is widely used in historical buildings in the city. It shows significant deterioration and weathering effects, principally in the parts where the tuff shows a coarse grain size. The petrographic, petrophysical, mineralogical and geochemical properties of the Loseros Tuff were analysed in order to determine the causes, effects, behaviour and response to deterioration of this volcanic rock. The results of the investigations suggest that in addition to the parameters like the grain size and the porosity properties, the pore radii distribution is decisive for the effectiveness of porosity and the water transport into the rock. It is recognized that once the liquid water invades the rock the dissolution of the matrix occurs, which is accompanied by a sudden moisture expansion favoured by the newly formed secondary porosity and the high content of expandable clay minerals.     

Monitoring of the temperature–moisture regime in St. Martin’s Cathedral tower in Bratislava

Buildings are often composed of materials with a porous structure. Moisture in the masonry has a destructive impact caused by cycles of drying–wetting and freezing–thawing. A new sensor principle for monitoring moisture in the masonry is presented herein. This sensor utilizes changes in the thermal conductivity of porous structures when they are filled with moist air, water, or ice depending on the existing thermodynamic conditions. Herein, the “hot-ball” method is used to measure the thermal conductivity. The moisture sensor is prepared for porous material corresponding to the parent material, whether it is rock, brick, or concrete. This parent sample is taken from a borehole drilled into the wall. Methodology for moisture sensor calibration is also presented. Sensors were placed in the masonry walls of St. Martin’s Cathedral tower in the North, South, and West orientations. The sensors were placed in the plaster and bricks at depths up to 60 mm in the wall surface, just below the window sill. The temperature–moisture regime was monitored from August 19th, 2011 to March 30th, 2012. Changes in temperature and moisture were then correlated with meteorological data.     

Prediction of weathering by thermal degradation of a coarse-grained marble using ultrasonic pulse velocity

Engineering properties of building stones can vary because of degradation by weathering agents. Thermal fluctuation is one of the most important agents on deteriorations such as sugaring, bowing, cracking and spalling of marble. As a result, physical and mechanical properties of marble used in the construction of old and/or modern structures are adversely affected by time. On the other hand, some properties of building stones are always required for decision of rehabilitation works. Several kinds of conventional tests have been suggested for characterization of stones, to measure their properties or to evaluate conservation or repair works. However, in most cases, sampling from historical buildings is not possible. Therefore, nondestructive testing methods are often suggested for the prediction of weathering grade of building stones. One of the most practical methods for similar purposes is ultrasonic pulse velocity measurement, which can be performed easily. The main goal of this study is attainment of sound empirical correlations between the ultrasonic pulse velocity and engineering properties of previously deteriorated marble. Experimental works were conducted on seven different specimen categories of a coarse-grained marble having different micro-crack frequencies induced by both cyclical heating–cooling and freeze–thaw actions. The experimental results indicated that physical and mechanical properties of Mu?la marble can be reliably estimated for different environmental cases by ultrasonic pulse velocities. P-wave velocities in dry and saturated cases are two sound indicators of both the apparent porosity and the coefficient of capillary absorption, and whereby the sugaring type of deterioration for coarse-grained marbles.     

Formulation and characterization of an appropriate lime-based mortar for use with a porous limestone

Several studies have shown that the degradation of architectural monuments constructed using Tuffeau stones from Val de Loire region of France over a period of time are often related to use of mortars that are not compatible with the Tuffeau stones. For this reason, it is important to ensure physico-chemical compatibility between Tuffeau and the mortar. To alleviate differences in compatibility characteristics, a mortar is prepared from hydrated lime and aggregates obtained from the crushing of Tuffeau stone and used in this study. The key parameters that influence the strength and durability characteristics such as mechanical resistance, water transfer properties, and physico-chemical properties were identified and studied. Based on these studies, recommendations are offered for the preparation of a more compatible mortar that can be used in the construction and restoration of monuments using Tuffeau stone.