Variations in trace element composition of pyrites in inactive chimneys from the SMAR 26°S hydrothermal field provide important insights into the genesis and evolution of volcanic-hosted hydrothermal mineralization. Petrographic observations of zoned chimney samples integrated with in-situ LA-ICP-MS analysis of morphologically different pyrites allowed the assessment of fluid evolution during the chimney growth. Pyrite varieties precipitated with increasing temperatures from the outermost chimney wall (zone A) through the intermediate zone (zone B) to the inner zone (zone C). At the late mature stage, pyrite precipitates as interstice pore fillings. The distribution of trace elements in pyrites across the chimney indicates a strong dependence on time, temperature, and associated sulfide minerals. Variations in the trace elements composition of the different pyrite varieties indicate that the hydrothermal system evolved from low-temperature low-chloride liquid-dominated fluids (enriched in Zn, Cd, Tl, Ag, Pb, Mn, Mo, and V) to higher temperature, vapor-dominated fluids (Cu, Au, Te, and Bi), and then to high-temperature fluids (Co and Se). In the waning stage of the hydrothermal system, circulating hot fluids in auxiliary conduits were depleted in most trace elements. The systematic variations in trace element compositions of hydrothermal fluids induced by changes in physicochemical conditions are properly governed by the law of normal distribution of trace elements. The LA-ICP-MS time-depth analysis indicate that Cu, Zn, Cd, Tl, Ag, Te, and Bi are related to micro-/nano-inclusions, whereas Co, Se, and Mo may occur as substitutions in pyrite lattice. The As, Pb, Au, and Sb show both modes of occurrences as substitutions and as inclusions. Adsorbed films on pyrites control the distribution of V and Mo. The incorporation processes of trace elements in pyrites change with fluid evolution during the chimney growth: trapping of micro-/nano-inclusions and surface adsorption is seen more frequently at the low-temperature stage, and lattice substitution mainly at the elevated temperature stages.
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