The physicochemical weathering of monumental dolostones, granites and limestones; dimension stones of the Cathedral of Toledo (Spain)

doi:10.1016/0048-9697(94)90498-7

Science of The Total Environment

Volume 152, Issue 2, 2 August 1994, Pages 179-188

https://doi.org/10.1016/0048-9697(94)90498-7 Get rights and content

Abstract

Physical and chemical response to weathering has been evaluated for the building stones (granites and carbonate rocks) of the Cathedral of Toledo, Spain. Several aspects have been studied in detail: distribution of porosity and its relation to the fabric within the weathered material, chemical composition of weathering-related surficial crusts, and the order of crystallization of the soluble salts derived from the weathering processes. In addition, the study places some emphasis on the calculation of the crystallization pressures of these salts within the porous material resulting from weathering. Highest pressures are due to gypsum crystallization and, in decreasing order, to: anhydrite, mirabilite, epsomite, bloedite, thenardite and kieserite.

References (12)

O. Söhnel
Electrolyte crystal-aqueous solution interfacial tensions from crystalization data
J. Crystal Growth
(1982)
E. Dapena et al.
Study of the limestone rock used in the construction of palaces in Madrid during 18th and 19th centuries
B.L. Davis et al.
Tables of experimental reference intensity ratios
Power Diffraction
(1988)
D.H. Everet
The thermodinamics of frost damage to porous solids
Trans. Faraday Soc.
(1961)
B. Fitzner et al.
Ueber Zusammenhange zwischen salzkristallisations druk und Porenradienverteilung
GP Newslett.
(1982)
M.C. Lopez de Azcona et al.
Degradation of building materials of the Toledo Cathedral (Spain)

There are more references available in the full text version of this article.

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Citation Excerpt :
This represents a temperature range during which the material remains liquid below the freezing point [14] and has become an important factor in quantifying the thermodynamic performance of PCM. [1–36] Na2SO4·10H2O generally melts incongruently, and Na2SO4 and saturated solution coexist over 32 °C. However, the high density of Na2SO4 (2.68 g/cm3) results in phase separation.
Phase change materials with an ability to store the renewable thermal energy find widespread applications as building materials and temperature control devices. In this study, a lightweight and energy-efficient temperature regulating material based on the sandwich structure of Na₂SO₄·10H₂O, expanded vermiculite and magnesium oxychloride cement has been reported. The composite material responded in the range 20–40 °C and extended the heating and cooling period of the indoor temperature. The developed material exhibited an improved application performance as compared to the traditional heat preservation materials. Further, the supercooling of Na₂SO₄·10H₂O/expanded vermiculite was determined to be 1.20 °C, along with shape stability. Different synthesis methods and phase change materials with cement were explored to minimize the degradation of the thermal regulation performance, and the sandwich structure was observed to exhibit the optimal performance. Owing to the low thermal conductivity of Na₂SO₄·10H₂O/expanded vermiculite and magnesium oxychloride cement, the extended holding time of the indoor temperature was observed. The developed material exhibits significant potential for future applications as self-regulating materials and novel temperature control devices in which the optimal thermo-physical properties are desirable.
The inhibition of crystal growth of mirabilite in aqueous solutions in the presence of phosphonates
2016, Journal of Crystal Growth
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Weathering damage of cultural heritage buildings and monuments and of modern constructions is a complicated process to which a number of factors contribute including physical, chemical and biological factors [1–7].
The formation of sodium sulfate decahydrate (Mirabilite) has been known to cause serious damages to structural materials both of modern and of historical buildings. Methods which can retard or completely suppress the development of mirabilte crystals are urgently needed especially as remedies or preventive measures for the preservation of the built cultural heritage. In the present work we present results on the effect of the presence of phosphonate compounds on the kinetics of crystal growth from aqueous supersaturated solutions at 18 °C using the seeded growth technique. The phosphonate compounds tested differed with respect to the number of ionizable phosphonate groups and with respect to the number of amino groups in the respective molecules. The crystal growth process was monitored by the temperature changes during the exothermic crystallization of mirabilite in the stirred supersaturated solutions. The crystal growth of mirabilite in the presence of: (1-hydroxyethylidene)-1, 1-diphosphonic acid (HEDP), amino tri (methylene phosphonic acid) (ATMP), hexamethylenediaminetetra (methylene)phosphonic acid (HTDMP), and diethylene triamine penta(methylene phosphonic acid)(DETPMP) over a range of concentrations between 0.1–5% w/w resulted in significant decrease of the rates of mirabilite crystal growth. All phosphonic compounds tested reduced the crystallization rates up to 60% in comparison with additive-free solutions. The presence of the test compounds did not cause changes of the mechanism of crystal growth which was surface diffusion controlled, as shown by the second order dependence of the rates of mirabilite crystal growth on the relative supersaturation. The excellent fit of the measured rates to a kinetic Langmuir-type model suggested that the activity of the tested inhibitors could be attributed to the adsorption and subsequent reduction of the active crystal growth sites of the seed crystals. In all cases, the inhibitory activity was reduced with increasing solution supersaturation, while the presence of DETPMP, which showed the best inhibition activity, showed the least reduction of inhibition with increasing supersaturation.
The origin of Mg sulphate and other salts formed on pure calcium carbonate substrate - Tufa stone blocks built into the Gradac Monastery, Serbia
2015, Construction and Building Materials
Citation Excerpt :
This finding indicates that larger amounts undoubtedly lead to more severe damage [9]. The source of magnesium required for these salts to form is generally related to the composition of the building material, which is commonly dolostone or magnesium-rich limestone [8,10–12], and mortar [13,14]. The stone facades of “The Holy Virgin” church from the 13th century in the southwestern part of Serbia were selected to investigate the origin of Mg-salts because of the complexity of the exterior and interior environment, i.e., the geological surrounding, construction material and history.
Epsomite and hexahydrate occur in the form of efflorescence on the church walls made of pure calcium carbonate – tufa stone. A few sources of magnesium are responsible for the precipitation of Mg-salts at the block surfaces: lime mortar with Mg-rich aggregates, repair lime cement mortar, the dolostone of the rubber core, and the monastery basement composed of Mg-rich rocks. Possible sources of sulphate are: repair lime cement mortar and soil solution. The permanent presence of different solution types in the tufa pore system enabled the precipitation of salts in the following order: calcite/dolomite, gypsum, Mg-sulphate phases, syngenite and blodeite.
Deterioration of dolostone by magnesium sulphate salt: An example of incompatible building materials at Bonaval Monastery, Spain
2009, Construction and Building Materials
Since its abandonment 185 years ago, the XII century Santa Maria de Bonaval Monastery located in Guadalajara (Spain) has suffered significant deterioration: first the roof was lost, followed by partial collapse of the walls, moisture infiltration and extensive loss of stone surfaces due to salt weathering. This case study is a clear example of the incompatibility of some building materials: in this case, the combination of sulphate-bearing mortars and magnesium-rich stone and mortars leading to extensive weathering by magnesium sulphate crystallization. Samples of plaster, bedding and core mortars, stone fragments and flakes, salt crust and powders were collected, as well stone samples from the historic quarries located close to the Monastery. Characterization by XRD (X-ray diffraction), ESEM-EDS (environmental scanning electron microscopy with energy dispersive X-ray spectroscopy) shows that the most important stone-type used in the structure, dolostone, is mainly affected by magnesium sulphate salts (epsomite, MgSO₄ · 7H₂O), although other salts as kalicinite (KHCO₃) and mercallite (KHSO₄) were also detected. The connected porosity and pore size distribution determined by mercury intrusion porosimetry and capillarity behaviour suggest that the core mortar could easily be dissolved and the stone, plaster and bedding mortars are able to transport infiltrating solutions, giving rise to the precipitation of magnesium sulphate in the mortar joints and over the surface of the stone. Due to their chemical incompatibility, the combination of sulphate and magnesium-bearing mortars and stone with high magnesium content appears to be problematic and should be avoided in future restoration work.
Salt-induced decay in calcareous stone monuments and buildings in a marine environment in SW France
2003, Construction and Building Materials
Salt weathering can be a hazard with significant cultural and economic implications. Salt-induced deterioration of architectural heritage is considered to be accelerated drastically in marine environments. This article investigates the weathering mechanisms and weathering forms in two calcareous stone types used in monuments and buildings on the SW coast of France. The mineralogical, chemical, textural and pore-system characteristics of freshly quarried and decayed stones from quarry, monuments and buildings were determined, and salts loading identified. The stones’ resistance against salt weathering was estimated by comparing calculated crystallisation pressures, which are function of the pore size distribution, with the tensile strengths measured by Auger [Alteration des roches sous influence marine; degradation des pierres en oeuvre et simulation acceleree en laboratoir. These Doctorat d'Etat es Siences. Universite de Poitiers, France (1987)]. Results show that Crazannes sparite and La Pallice micrite behave differently with respect to water and salt-spray absorption and local salt precipitation since their pore networks, which control hydric properties, are different. Therefore, diverse weathering patterns due to salt crystallisation pressures were identified in the stones as influenced largely by their pore size distribution: alveolar weathering and granular disintegration in the sparite vs. flaking and micro-fissuring in the micrite. These mechanisms operate in response to salt inputs from a variety of sources—mainly marine aerosols and atmospheric pollution—as corroborated by the so-called enrichment factors (EFs). Wind is believed to trigger alveolar weathering in the heterogeneous sparite. Short-term observations in La Pallice micrite show rapid salt-induced breakdown through ‘fatigue’ effects. Determining factors involved in stone deterioration is important in the design of proper interventions for protecting historic buildings.
How does sodium sulfate crystallize? Implications for the decay and testing of building materials
2000, Cement and Concrete Research
The fundamental behavior of sodium sulfate crystallization and induced decay in concrete and other building materials is still poorly understood, resulting in some misinterpretation and controversy. We experimentally show that under real world conditions, both thenardite (Na₂SO₄) and mirabilite (Na₂SO₄·10H₂O) precipitate directly from a saturated sodium sulfate solution at room temperature (20°C). With decreasing relative humidity (RH) and increasing evaporation rate, the relative proportion of thenardite increases, with thenardite being the most abundant phase when precipitation occurs at low RH in a porous material. However, thenardite is not expected to crystallize from a solution at T<32.4°C under equilibrium conditions. Non-equilibrium crystallization of thenardite at temperatures below 32.4°C occurs due to heterogeneous nucleation on a defect-rich support (i.e., most porous materials). Anhydrous sodium sulfate precipitation is promoted in micropores due to water activity reduction. Fast evaporation (due to low RH conditions) and the high degree of solution supersaturation reached in micropores before thenardite precipitation result in high crystallization pressure generation and greater damage to porous materials than mirabilite, which crystallizes at lower supersaturation ratios and generally as efflorescence. Data from the environmental scanning electron microscope (ESEM) show no hydration phenomena following wetting of thenardite; instead, thenardite dissolution occurs, followed by thenardite plus mirabilite crystallization upon drying. These results offer new insight into how damage is caused by sodium sulfate in natural geological, archaeological, construction and engineering contexts. They also help explain some of the controversial results of various commonly used sodium sulfate crystallization tests.

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The physicochemical weathering of monumental dolostones, granites and limestones; dimension stones of the Cathedral of Toledo (Spain)

Abstract

J. Crystal Growth

Study of the limestone rock used in the construction of palaces in Madrid during 18th and 19th centuries

Tables of experimental reference intensity ratios

Power Diffraction

The thermodinamics of frost damage to porous solids

Trans. Faraday Soc.

Ueber Zusammenhange zwischen salzkristallisations druk und Porenradienverteilung

GP Newslett.

Degradation of building materials of the Toledo Cathedral (Spain)