Trace-element distribution and ore-forming processes in Au-Ag-rich hydrothermal chimneys and mounds in the TA25 West vent field of the Tonga Arc

We report detailed mineralogy and geochemistry of hydrothermal mounds and chimneys in the TA25 West vent field (TA25 WVF), a newly discovered magmatic-hydrothermal system in the Tonga (Tofua) arc. Chimney samples are classified as sulfate- or sulfide-rich, based on major sulfide, sulfosalt, and sulfate minerals. The former type represents a simple mineral assemblage of predominance of anhydrite/gypsum + barite + pyrite, whereas the sulfide-rich chimneys show three different stages of mineralization with decreasing fluid temperature: sphalerite-pyrite dominated stage I, sphalerite-sulfosalts dominated stage II, and stage III is dominated by seawater alteration. Mound samples are characterized by sulfide assemblages and paragenesis similar to those of sulfide-rich samples, but abundant chalcopyrite indicates a relatively high-temperature mineralization. The chimney and mound samples are enriched in Au (average 9.2 ppm), Ag (297 ppm), As (1897 ppm), Sb (689 ppm), Hg (157 ppm), and Se (34.6 ppm). LA-ICP-MS and FE-TEM studies indicate that most of these elements occur in sulfides or sulfosalts in solid solution, although some occur as nanoparticles. This is mainly controlled by the combined effects of fluid conditions (temperature and redox state) and influx of ambient seawater. Petrography and trace-element compositions of sulfides and/or sulfosalts suggest that most concentrations of Au and Ag in the TA25 WVF result from the precipitation and/or adsorption of Au-Ag-bearing nanoparticles on rapidly crystallized sulfides, the substitution of Au and Ag in sulfide and/or sulfosalt minerals, and the saturation of Ag in hydrothermal fluids during late, relatively low-temperature mineralization (< 150 degrees C). The maximum measured temperature (242 degrees C) of venting fluids and calculated formation temperatures of sphalerite (229-267 celcius) are below the boiling temperature of seawater at the depths (966-1096 m) of the TA25 WVF, suggesting fluid boiling had little effect on Au-Ag-rich mineralization in the TA25 WVF. The presence of enargite-tetrahedrite-tennantite assemblages, high concentrations of magma-derived elements (e.g., Au, Ag, As, Sb, Hg, and Se), low delta S-34 values (2.1 to 4.3 parts per thousand) of sulfide minerals relative to the host rocks, and the distribution of CO2-rich hydrothermal plumes (500 to 1000 ppm) suggest that the TA25 WVF is a submarine hydrothermal system influenced by a magmatic contribution in an arc setting. Our results indicate that the magmatic contribution is most likely to play an important role in supplying various metals, including Au and Ag, to the TA25 WVF. Subsequently, the rapid crystallization of sulfides induced by abundant fluid-seawater mixing significantly contributes to the precipitation of Au-Ag-rich mineralization.