Abstract A major concern motivating research in acid rain materials effects has been the potential for damage to cultural heritage, particularly outdoor marble and bronze sculpture. However, a combination of field and laboratory studies has failed to show a correlation between rain pH and loss of materials. In order to understand this counterintuitive lack of acid rain effect, an aqueous geochemical modeling approach was used to analyze rain runoff chemistry for the relative importance of acid rain neutralization, dry deposition, and in the case of marble, natural carbonate dissolution. This approach involved the development of pH – SO4 ²⁻ phase diagrams for marble (calcium carbonate) and bronze (copper) under ambient environmental conditions. This then enabled reaction path modeling of the acid neutralization process using the pH range typically found in wet deposition (3.5–6). The results were for marble that the theoretical maximum amount of Ca²⁺ ion that could be lost due acid rain neutralization would be 0.158 mmol/l compared to 10.5 mmol/l by dry deposition, and for bronze, the Cu²⁺ ion losses would be 0.21 mmol/l and 47.3 mmol/l respectively. Consequently dry deposition effects on these materials have the potential to dominate over wet deposition effects. To test these predictions the geochemical models were applied to examples of data sets from mass balance (runoff vs rainfall) studies on a marble statue in New York City and some bronze memorial plaques at Gettysburg PA. Although these data sets were collected in the early 1980s they remain valid for demonstrating the mass balance method. For the marble statue, the mean Ca²⁺ losses by dry deposition was about 69% of the total compared 0.3% for acid rain neutralization, which was less than the natural carbonate dissolution losses of 0.8%. For the bronze, the mean Cu²⁺ losses were 70.6% by SO4 ²⁻ dry deposition and 23% by NO3 ⁻ dry deposition compared to 6.4% by acid rain neutralization. Thus for both cases the wet deposition component was less than the variability of the dry deposition components, which explains the observed lack of correlation between the rain pH and the material losses. In addition, for the marble case, there was evidence for HCl acid vapor attack resulting from nitric acid/sea salt interactions and for bronze, ammonium ion may be important. In both cases, significant imbalances suggested that unmeasured organic acids may have a significant effect.

Highlights • Most significant sculptural materials are carbonate stone and bronze. • Weathering processes due to rain can be measured by the mass balance method. • Geochemical modeling can be applied to analyze mass balance data. • Rain acidity effects are negligible compared to dry deposition. • Organic acids may also have a significant effect.