Discolouration of Gold Decorations

Discoloured 18-carat gold decorations from Sweden have been analysed by scanning electron microscopy with energy dispersive X-ray spectroscopy and X-ray electron spectroscopy (XPS)/electron spectroscopy for chemical analysis (electron spectroscopy).The original gold composition was close to 75% gold, 13% silver, and 12% copper. After manufacture, many details were boiled in sulphuric acid. As a consequence of this, the surfaces are irregular and porous with a gold concentration around 90% and with less than 1% copper. With XPS the outermost 10–20 atomic layers could be examined. No copper was present here, and the silver concentration was significantly higher. Also carbon, sulphur, oxygen, and (in one case) chlorine were present. The valence numbers indicated that gold only occurred in its metallic state, while silver (as Ag⁺) was preferably associated with sulphur to form black silver sulphide (Ag₂S). The grey discolorations are basically due to silver sulphide and organic dirt. Sometimes green, violet, and ‘copper-shining’ colours occur, presumably as a result of light refraction phenomena.