Cyanide is a significant cost in gold processing, as well as an environmentally sensitive issue. It has been suggested that precipitation of cyanide from leach liquors as copper-iron-cyanide compounds such as Cu2Fe(CN)6 may account for part of the total cyanide consumption. This may be especially true for ores that are rich in both copper and iron minerals. Ammonia addition has been shown to decrease the cyanide consumption by copper. Cu2Fe(CN)6.xNH3 precipitates have also been postulated to form during conventional cyanide detoxification processes, using oxidants such as SO2/air, with ammonia arising as a breakdown product from the oxidation of free cyanide. The present work has examined the conditions under which such precipitates may form, particularly in gold plant process and detoxification liquors. Ammonia and pH were found to have a large effect on the extent of precipitation. The compounds that were formed were found to comprise mainly Cu2Fe(CN)6.7H2O, as well as a range of NH3-bearing variants. The stabilities of the various precipitates are important from an environmental perspective. The long-term stability of copper ferrocyanide precipitates in tailings dams may be a problem under alkaline conditions and when some free cyanide is present, elevating the measured total cyanide in solution significantly. Case studies including data from actual plants are also considered, and the importance of these effects is reaffirmed from these results.