A Novel Approach to Carbonate Stone Conservation: Induced Calcium Oxalate Formation Through the Application of Ammonium N-Ethyloxamate (AmEtOxam) on White Carrara Marble

Simone Murgia

First

;M. Carla Aragoni

Second

;Gianfranco Carcangiu;Laura Giacopetti;Domingo Gimeno Torrente;Vito Lippolis;Eleonora Loi;Paola Meloni;Antonia Navarro Ezquerra;Enrico Podda;Anna Pintus;Riccardo Serra;Massimiliano Arca

Last

2026-01-01

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Abstract

Ammonium N-ethyloxamate (AmEtOxam) was synthesized, fully characterized by microanalytical and spectroscopic means, and assayed as a precursor of calcium oxalate, acting as a protecting agent for white Carrara marble. The monohydrate form of AmEtOxam shows a water solubility of 1.5 mol·L−1 (~23% w/w), significantly higher than that of common calcium oxalate precursors (CaOx), such as ammonium oxalate (0.4 mol·L−1, ~5% w/w). While AmEtOxam is stable in water solution and in the solid state in its monohydrate form, during the application on carbonate stone it undergoes a complete hydrolysis resulting in the formation of a uniform weddellite layer (CaC2O4·2H2O) on carbonate stone surfaces. Application of 5% w/w aqueous solutions by spraying, brushing, and immersion resulted in different effects. Spraying yielded the most balanced performance, improving mechanical strength, reducing water absorption, recovering superficial tension, and limiting chromatic alteration. Brushing achieved significant gain in surface hardness with minimal esthetic impact. Immersion most effectively reduced porosity and increased surface tension. These results, coupled with the negligible chromatic changes induced in all cases, make AmEtOxam a promising candidate for the conservation of stone cultural heritage.