Effects of acidic deposition on the erosion of carbonate stone — experimental results from the U.S. National Acid Precipitation Assessment Program (NAPAP)

Abstract

One of the goals of NAPAP-sponsored research on the effects of acidic deposition on carbonate stone has been to quantify the incremental effects of wet and dry deposition of hydrogen ion, sulfur dioxide and nitrogen oxides on stone erosion. Test briquettes and slabs of freshly quarried Indiana limestone and Vermont marble have been exposed to ambient environmental conditions in a long-term exposure program. Physical measurements of the recession of test stones exposed to ambient conditions at an angle of 30° to horizontal at the five NAPAP materials exposure sites range from ∼ 15 to ∼ 30 μm yr⁻¹ for marble, and from ∼ 25 to ∼ 45 μm yr⁻¹ for limestone, and are approximately double the recession estimates based on the observed calcium content of run-off solutions from test slabs. The difference between the physical and chemical recession measurements is attributed to the loss of mineral grains from the stone surfaces that are not measured in the run-off experiments. The erosion due to grain loss does not appear to be influenced by rainfall acidity, however, preliminary evidence suggests that grain loss may be influenced by dry deposition of sulfur dioxide between rainfall events. Chemical analyses of the run-off solutions and associated rainfall blanks suggest that ∼ 30% of erosion by dissolution can be attributed to the wet deposition of hydrogen ion and the dry deposition of sulfur dioxide and nitric acid between rain events. The remaining ∼ 70% of erosion by dissolution is accounted for by the solubility of carbonate stone in rain that is in equilibrium with atmospheric carbon dioxide (“clean rain”). These results are for marble and limestone slabs exposed at an angle of 30° from horizontal. The relative contribution of sulfur dioxide to chemical erosion is significantly enhanced for stone slabs having an inclination of 60° or 85°. The dry deposition of alkaline particulate material has a mitigating effect at the two urban field exposure sites at Washington, DC, and Steubenville, OH.