Suflur isotopic analyses of hydrothermal chimneys and coexisting fluids collected from hot vent areas at 21 ¿N, East Pacific Rise, indicates Δ34S values for sulfide minerals of 0.9--6.2% and for aqueous H2S of 1.3--5.5%0. The chemical processes resulting in mineral zoning of chimney structures are a controlling influence on Δ34S variation within individual chimneys.

In general, coarsely crystalline chalcopyrite, which lines chimney interiors, is depleted in 34S relative to exterior ZnS (either sphalerite or wurtzite). Chalcopyrite which formed by replacement of other sulfides has higher sulfur isotope values than chalcopyrite which precipitated directly from hydrothermal fluid. Bornite and other Cu-rich sulfides, which occur as thin layers replacing the outer margins of massive chalcopyrite zones, have the highest Δ34S values of any 21 ¿N samples, ranging from 5.2%0 to 6.2%0. The significant 34S enrichment in bornite requires reduction of isotopically heavy seawater-derived sulfate in the chimney walls. Vent fluid Δ34SH2S values are similar to Δ34S values of inner wall chimney sulfides for seven of 11 samples.

In other samples, aqueous H2S is enriched isotopically in 34S compared with coexisting sulfides, suggesting admixture of H2S derived from reduced seawater sulfate. The Δ34S value of end-member hydrothermal fluid at 21 ¿N is about 1.0--1.5%0, which is somewhat higher than basaltic sulfide, the main source of sulfur in the hydrothermal system. This 34S enrichment apparently is due to sulfate reduction in the deep hydrothermal system during conversion of basaltic pyrrhotite to pyrite. The South West (SW) vent field has significantly higher average Δ34S values (3.1%0) compared with the other 21 ¿N vent fields. The SW field is situated on the edge of a lava collapse structure, promoting development of an extensive feeder zone which is the site of near-surface sulfate reduction during redissolution of previously deposited anhydrite. The Δ34S values for chimney sulfides and vent fluid H2S which are higher than about 3%0 for SW samples and higher than about 2%0 for the other vents reflect incorporation of addidional reduced seawater sulfate in the chimney environment.