The early stage of copper patination, which occurs when copper is exposed to the atmosphere, was investigated by exposing copper plates for one month in urban, rural/coastal, hot springs, suburban, and volcanic areas. The exposures experiment started in summer or autumn. The patinas that formed during the one-month exposure were characterized using X-ray diffraction (XRD), X-ray fluorescence analysis, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and glow discharge optical emission spectroscopy (GDOES). The XRD patterns revealed that cuprite (Cu2O) and posnjakite (Cu 4SO4(OH)6-H2O) formed on the copper exposed in all areas, except the hot springs area. This is the first report of posnjakite forming on copper exposed for one month in benign environments. The XRD pattern revealed only cuprite on the copper exposed in the hot springs area although copper sulfide (CU2S) was found in the cathodic reduction curve. The sulfur 2p XPS spectra of copper exposed in the urban, rural/coastal, and volcanic areas mainly showed a sulfate component, whereas that of copper exposed in the hot springs area showed both sulfide and sulfate components. The former reflected the formation of posnjakite ; the latter reflected the oxidation of sulfide during exposure. In contrast, the chlorine 2p XPS spectra revealed that the chlorine existed as chloride. The SEM observation revealed that the surface morphology differed between exposure sites. GDOES depth profiling analysis revealed a difference in the distributions of sulfur and chlorine in the early stage of copper patination. The sulfur was located in the upper part of the patina, whereas the chlorine penetrated the patina. The oxidized sulfur species lowered the pH of the surface electrolyte, and this accelerated the dissolution of cuprite. They also formed posnjakite, which roughened the surface. The reduced sulfur species lowered the pH of the surface electrolyte and formed copper sulfide. The chlorine dissolved the cuprite forming copper chloride complex. This changed the chlorine depth profile.
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