Trace and minor elements in the ore minerals: An assessment of geochemical distribution in overprinting epithermal on porphyry mineralization at Chodarchay, NW Iran

Abstract

The Chodarchay overprinting epithermal on porphyry mineralization occurs in the Tarom-Hashtjin subzone of the Alborz magmatic arc in northwestern Iran. Rock units include intrusions (phases I and II) and volcano-volcaniclastic rocks. The alteration types consist of potassic, phyllic, argillic, and propylitic. The porphyry type is mostly accompanied by potassic alteration. The Chodarchay Fault implies two extensional and compressional mechanisms. The porphyry type is associated with the extensional and the epithermal type with the compressional stage of the fault. Mineralization occurred mainly inside the Eocene volcanic and volcano-sedimentary rocks; some ores are associated with the Late Eocene quartz monzonite. The mineralization is divided into three zones from depth to surface: 1) Hypogene sulfide zone (deep); 2) Enriched supergene sulfide zone (near-surface); 3) Oxidized and leached zone (surface). The major sulfide minerals consist of chalcopyrite, pyrite, sphalerite, and galena. Based on the results of the new analyses, chalcopyrite hosts Ag as a solid-solution and contains Ag-rich Bi-sulfosalt micro-inclusions. Non-constant Cd/Zn ratio in the chalcopyrite can indicate varying physiochemical conditions during its crystallization. Low As contents in the pyrite caused relatively clean pyrite with very few elements. The Ni concentrations in the pyrite imply that it was sourced from mantle mafic–ultramafic rocks. Sphalerite is the only Au-host mineral among the sulfide minerals as a nano-mineral phase. Solid-solution Ag exists in the sphalerite. The sphalerite Fe/Zn ratios show that it was precipitated between 220 and 280 °C. Silver and Bi have the highest measured concentrations among all analyzed elements in the galena, mainly partitioning within the galena, but Hg and Cd are abundant in the sphalerite. Bornite is one of the major carriers of Ag and Bi. Silver and Bi exhibit considerable variations in the Cu-(Fe) sulfides. A new occurrence of sulfosalt minerals was identified at Chodarchay (N = 14). The discovered Bi-sulfosalts include cuprobismutite group minerals (cuprobismutite, hodrushite, and paderaite), aikinite-bismuthinite series (aikinite and friedrichite), emplectite, makovickyite, galenobismutite, gustavite, heyrovskyite, neyite, cupropavanite; and As-Sb-bearing Cu sulfosalts (watanabeite and colusite). This number of sulfosalts had not previously been reported from any of the Tarom or Alborz deposits or mines. The Au-Ag occurrence was reported from the neyite, emplectite, and gustavite. The Ag-rich minerals crystallize from fractionated fluids that cooled during rising. Silver-carrier sulfosalts may have been exsolution from pre-existing Ag-bearing chalcopyrite in the cooling system. Most of the Ag-bearing sulfosalt minerals formed at the margins and fractures of the chalcopyrite, indicating that the cooling started from these points. Thus, Ag at Chodarchay is hosted inside Cu-(Fe) sulfides, the significant part of them being chalcopyrite and Ag-rich sulfosalt micro-inclusions inside the chalcopyrite. The fluid temperature for the Ag and chalcopyrite precipitation is from 200 to 350 °C. Bismuth assemblages precipitated at > 350 °C. The cuprobismutite group crystallizes at temperatures > 300 °C. The supergene process and rare secondary enrichment of Ag and Au took place in the oxidation zone; this enrichment is dependent on the presence of manganese. Based on the fire-assay results, the concentration of gold is greater at shallower depths.