How does acid precipitation affect marble and limestone buildings?

You might expect that sheltered areas of stone buildings and monuments would not be affected by acid precipitation. However, sheltered areas on limestone and marble buildings and monuments show blackened crusts that have spalled (peeled) off in some places, revealing crumbling stone beneath. This black crust is primarily composed of gypsum, a mineral that forms from the reaction between calcite, water, and sulfuric acid. Gypsum is soluble in water; although it can form anywhere on carbonate stone surfaces that are exposed to sulfur dioxide gas (SO₂), it is usually washed away. It remains only on protected surfaces that are not directly washed by the rain. Gypsum is white, but the crystals form networks that trap particles of dirt and pollutants, so the crust looks black. Eventually the black crusts blister and spall off, revealing crumbling stone.

When marble is exposed to acidic rain, sharp edges and carving details gradually become rounded. Antefixes, roof of the Philadelphia Merchants' Exchange (built in 1832).	Blackened crusts on sheltered portions of the limestone Chicago Tribune Building, Chicago, Illinois.
Formed as a result of air pollution, gypsum alteration crusts have blackened, blistered, and spalled from a marble baluster at the Organization of American States building, Washington, D.C.	Scanning electron microscope photograph of gypsum crystals with dirt and pollution particles trapped by the network of crystals. The scale bar is 10 micrometers long.
A marble column at the Merchants' Exchange in Philadelphia shows loss of material where the stone is exposed to rain and blackening of the stone surface where the stone is sheltered from rain.