Marble deterioration

This report describes early measurements of the deterioration of limestone and marble building stones by acidic components of air pollution and acid rain. This onsite technique allows measurement of carbonate-rock deterioration under a wide range of ambient conditions. Limestone and marble deterioration have been related quantitatively to acid deposition to the rock surface. The procedures described here appear to have general applicability for developing reliable rock-damage relations for environmental contaminants. 

Feddema JJ, MererdingTC (1991) Marble deterioration in the urban atmosphere. In Baer NS, Sabbioni C, Sors AI (eds) Science, technology and European cultural heritage. Butterworth-Heinemann, Oxford/England, pp 443 46 Fenchel T, Finlay BJ (1995) Anaerobic environments. In Fenchel T, Finlay BJ (eds) Ecology and evolution in anoxic Worlds. Oxford University Press, New York, pp 1-31... 

Del Monte, M., Sabbioni, C. and Vittori, O. (1981). Airborne carbon particles and marble deterioration. Atmos. Env., 15 645-652. 

Describe possible mechanisms for the deterioration of marble statuary. 

Acid deposition and the associated particulate nitrates and sulfates are implicated in the deterioration of certain sensitive ecosystems, decreased visibility, negative human health effects, and increased degradation of certain stone building materials and cultural resources, especially those made of limestone and marble. Fine particulate nitrate and sulfate particles... 

Acid rain harms the environment in a number of ways it dissolves many rocks and metals, alters the composition of soils, groundwaters, and lakes, and alters the environmental conditions of living organisms. Acid rain is also particularly harmful to ancient objects and structures, as it plays an important role in their deterioration and sometimes total destruction. Unprotected limestone, marble, and sandstone, all of them widely used in ancient times for building and making statuary, are disintegrated by acid rain, which... 

When alumina is combined with the silica, forming a natural clay, a much more compact and fusible compound is formed with the lime than when the silica is alone. Indeed, it has been observed as a general principle, that tire point of fusion is materially affected by the relation and number of bases the whole materials contain thus, a more liquid scoria is obtsined by the addition of a limestone containing magnesia than with a pure limestone. But experience is against the use of a magnesieu limestone, because it deteriorates the iron produced, while the purity of the metal iB the primary consideration. That which contains much silica should also be used sparingly, as silica combines with the iron and injures its quality, -The purest limestones are the most suitable for flux. Common marble is nearly a pnre carbonate of lime but is too rare and expensive to be used as a flux. 

Among the many dramatic effects of acid rain are the extinction of fish from acidic lakes throughout parts of the northeastern United States, Canada, and Scandinavia, the damage to forests throughout much of central and eastern Europe, and the deterioration everywhere of marble buildings and statuary. Marble is a form of calcium carbonate, CaC03, and, like all metal carbonates, reacts with acid to produce C02. The result is a slow eating away of the stone. 

The effect of pH on the solubility of CaC03 has important environmental consequences. For instance, the formation of limestone caves, such as Mammoth Cave in Kentucky, is due to the slow dissolution of limestone (CaC03) in the slightly acidic natural water of underground streams. Marble, another form of CaC03, also dissolves in acid, which accounts for the deterioration of marble monuments on exposure to acid rain (Interlude, pages 650-651). 

Materials and Structures. Building materials have become soiled and blackened by smoke, and damage by chemical attack from acid gases in the air has led to the deterioration of many marble statues in western Europe. Metals are also affected by air pollution for example, S02 causes many metals to corrode at a faster rate. Ozone is known to oxidize rubber products, and one of the effects of Los Angeles smog is cracking of rubber tires. Fabrics, leather, and paper are also affected by S02 and sulfuric acid, causing them to crack, become brittle, and tear more easily. 

In addition to low pH values, acid rain containing nitrates can oxidize materials such as copper or iron. Other consequences of acid rain include the deterioration of marble or any carbonated exterior material due to the decomposition reaction ... 

What is the chemistry of the deterioration of marble by sulfuric acid Marble is produced by geological processes at high temperatures and pressures from limestone, a sedimentary rock formed by slow deposition of calcium carbonate from the shells of marine organisms. Limestone and marble are chemically identical (CaC03) but differ in physical properties because limestone is composed of smaller particles of calcium carbonate and is thus more porous and more workable. Although both limestone and marble are used for buildings, marble can be polished to a higher sheen and is often preferred for decorative purposes. 

The damaging effects of acid rain can be seen by comparing these photos of a decorative statue on the Field Museum in Chicago. The photo on the left was taken c. 1920 the photo on the right was taken in 1990. Recent renovation has since replaced the deteriorating marble. 

One harmful effect of acid rain is the deterioration of structures and statues made of marble or limestone, both of which are essentially calcium carbonate. The reaction of calcium carbonate with sulfuric acid yields carbon dioxide, water, and calcium sulfate. Because calcium sulfate is marginally soluble in water, part of the object is washed away by the rain. Write a balanced chemical equation for the reaction of sulfuric acid with calcium carbonate. 

In the atmosphere, sulfur oxides can combine with water and oxygen to form sulfurous and sulfuric acids. The deposition of these acids causes corrosion or decomposition of materials such as limestone, marble, iron, and steel. The deterioration of building facades and monuments is one result of this worldwide problem. Flushing of the sulfur oxides from the air by precipitation (acid rain) can lead to acidification of lakes and sods, weakening or killing plants and animals. 

Many examples of acid-base reactions can be found in cooking, such as the soda-sour cream reaction in Little Men. In addition, the unfortunate result of acid rain (the formation of which we will discuss later) is that the acid in the rain reacts with the carbonates found in limestone and marble, which causes the deterioration of statues, some of which had managed to survive without corrosion for thousands of years before the advent of the industrial age. (But before one completely condemns the industrial age, it should be remembered that the bacteria of Black Death, smallpox, and syphilis also managed to survive for thousands of years before modem technology brought them to bay.) This ability of acid rain to dissolve marble brings up another property common to all acids and bases they are corrosive. 

The full methodology of retrospective analysis was applied for the case of marble tombstone deterioration in an urban and a remote cemetery near New York City (8,9). In this exercise it was found that our technique may estimate rural SO2 concentrations acceptably well, but it does not reproduce detailed structure of urban concentrations adequately. The main reasons are uncertainty about the effective release heights of sources and a lack of detailed local emission Information. For the purposes of metal corrosion, the current state of the retrospective reconstruction of environmental histories is not sufficiently quantitative to warrant extraction of damage functions. 

Husar, R.B., Patterson, D.E. (1985d). Marble tombstone deterioration in New York City area.Report to EPA Atmospheric Research Laboratory, Research Triangle Park, NC. 

Deterioration of brick masonry is a problem that has worried man ever since the first brick wall was constructed. It is interesting to remember that already by the first century A.D. bricks were considered more resistant to deterioration than marble., which had an estimated useful lifetime of about 80 years ( ). Today, the problem is still in study, if only due to the increased number of masonry structures. 

The deterioration of marble and limestone exposed both to anthropogenic acid deposition from the environment and to natural weathering is being assessed as one of the major activities of the Materials Effects Task Group of the National Acid Precipitation Assessment Program (NAPAP). There is much concern for the calcareous stone materials because of their widespread use as the exterior structure of commercial, institutional, and private buildings as well as in valued monuments and memorials. These calcium carbonate materials are especially sensitive to an acid environment. 

Reddy, M. Sherwood, S. Doe, B. "Limestone and Marble Dissolution by Acid Rain" Proceedings of 5th International Congress on Deterioration and Conservation of Stone, 1985. 

The section on masonry deterioration focuses on limestone, coquina, sandstone, marble, concrete, brick, and mortar as related to acid deposition effects on structures such as buildings and on cultural resources such as monuments. 

Figure 6 illustrates this phenomenon. Note that the angel under the dome has been rendered unrecognizable by the exfoliation of gypsum crusts formed by weathering. The angel in the open, on the other hand, has been much less severely deteriorated, although it is made of the same marble. 

Acid rain has many deleterious effects. It can destroy aquatic life in lakes and streams it can make soil so acidic that crops cannot grow and forests can be destroyed (see page 53) and it can cause the deterioration of paint and building materials, including monuments and statues that are part of our cultural heritage. Marble—a form of calcium... 

Air currents in the atmosphere carry the sulfuric acid and nitric acid many thousands of kilometers before they precipitate in areas far away from the site of the initial contamination. The acids in acid rain have detrimental effects on marble and limestone stmctnres, lakes, and forests. Throughont the world, monuments made of marble (a form of CaC03) are deteriorating as acid rain dissolves the marble. 

Thickett D, Lee NJ, Bradley SM (2000) Assessment of the performance of silane treatments applied to Egyptian limestone sculptures displayed in a museum environment. In Fassina V (ed) Proceedings of 9th international congress on deterioration and conservation of stone, Venice, Vol 2, 19-24 June. Elsevier Science, Amsterdam, pp 503-511 Toniolo L, Poll T, Castelvetro V, Manariti A, Chiantore O, Lazzari M (2002) Tailoring new fluorinated acrylic copolymers as protective coatings for marble. J Cult Herit 3(4) 309-316. doi 10.1016/S 1296-2074(02)01240-2... 

The appropriate values to be assigned to the stiffness coefficients k and k depend on the material of the drums. Since typical values for various materials are not provided in the literature, the assignment of these values is not easy. If experimental data are available, the coefficients can be calibrated against these data. However, such data are very few and concern specific materials only (usually marble). It is noted that loose contacts at the joints due to deteriorations of the contact surfaces might also affect the results. 

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