Hydrothermal alteration at the Phelps Dodge Archean volcanogenic massive sulfide deposit has converted rhyodacite and rhyolite footwall rocks into the following mineral assemblages: quartz-chlorite-albite-epidote ± sericite, quartz-chlorite ± sericite, chlorite ± seri- cite, and chlorite-talc ± stilpnomelane. Alteration at constant Al was initiated by hydration, addition of Fe + Mg, silicification, and leaching of Ca + Na which produced Al-saturated chlorites with a wide range of Fe/Fe + Mg ratios within the assemblage quartz-chlorite-albite-epidote ± sericite. With continued addition of Fe and less Mg, combined with extensive leaching of quartz, the chlorite became Al-undersaturated (quartz-chlorite-talc assemblage), and ultimately formed a rock composed essentially of chlorite. The chlorite-talc ± stilpnomelane assemblage is stable in late crosscutting veinlets and in the ore zone. Chlorites in the Si-Al-Mg-Fe system form a rectangular solid solution plane with limited substitution of Al for Si and extensive substitution of Fe for Mg. In Si-Al space the solid solution plane is outlined by Al saturation (presence of other Al-rich mineral) and Al undersaturation (presence of Al-poor or Al-free mineral) boundaries. Allv substitution for Si in the chlorites increases from 2.3 to 3.01 formula units (based on 8 Si + Allv) with Fe/Fe + Mg, whereas Alvl occupancy decreases from 2.88 to 2.65. The valence charge balance is compensated by octahedral site vacancies or by the conversion of Fe+2 to Fe+3. The Allv content of chlorite also increases with temperature. Chlorites on the Al-saturated boundary of the solid solution field form a potentially useful geothermometer: T °C = 106A1,V +18; AlIV is corrected for changes with the Fe/Fe + Mg ratio as: Allv corrected = Allv + 0.7 Fe/Fe + Mg. The Fe/Fe + Mg ratios of bulk rock and contained chlorite correlate well. Birefringence colors of the chlorite change from green to brown, violet, and Berlin Blue as Fe/Fe + Mg changes from 0.18 to 0.64. The Fe/Fe + Mg variation apparently depends largely on the proportions of Mg-rich seawater and Fe-rich hydrothermal fluid in the altering brine. © 1987 Society of Economic Geologists, Inc.