Study on the mechanism of the black crust formation on the ancient marble sculptures and the effect of pollution in Beijing area

In Beijing area, the precious stone objects often suffer from the black crusts on the specific parts of the objects, in order to understand the forming mechanism of the black crusts, samples from the stone sculptures in Beijing Stone Carving Art Museum, ZHIHUA Temple and Museum of Western Zhou Yandu Relics were taken and studied. Nondestructive measurement was carried out firstly to acquire main elements of the samples by portable X-ray spectrum (pXRF). Morphology and microstructure of typical black crust samples were examined by ultra-depth of field microscope (UDFM) and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS). Compositions of black crusts and body rocks were evaluated with X-ray diffraction (XRD), Raman spectra and mapping. Inductively coupled plasma optical emission spectrometry (ICP-OES) and pyrolysis-gas chromatography/mass spectrometry (Py-GCMS) were used to identify the major pollution sources leading to the black crusts. Through this study, the composition of the black crusts was revealed. Different gypsum crystals and carbonaceous species were found. Pollutant elements analysis and pyrolysis products provide indicators of the pollution sources. As consequence of strong photochemical oxidation processes and the high temperature from June to September in Beijing, more acid rain precursors can be formed. Frequent sulphation process occurs on the CaCO(3)/CaMg(CO(3))(2) surface. Combining morphology results and atmospheric data, the formation of black crusts in Beijing can be deduced.