Photochemically induced reactions of dicyanomercury(II) and potassium tetracyanomercurate(II) in alkaline aqueous solutions were investigated in detail. The studies were conducted in the presence or absence of a titanium(IV) oxide semiconductor photocatalyst utilizing sunlight as the irradiation source. It was established that the cyanide ion liberated from the thermodynamically stable mercury-cyano species can be photocatalytically oxidized via cyanate and nitrite to nitrate. In addition, the process removes over 99 mol% of mercury from the solution. In the absence of the photocatalyst, no photoproducts were detected and mercury remained in solution. The results obtained may have ramifications for the use of solar power for the efficient treatment of large quantities of precious metals mill tailings wastes containing various cyanide species. In addition, in order to follow the fate of cyanide in these experiments, a novel gas-diffusion flow injection analysis system for the determination of cyanide from the thermodynamically stable mercury-cyano complexes was utilized.

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