Isotopic evidence for the source of sulfur in the Upper Freeport coal bed (west-central Pennsylvania, U.S.A.)

Abstract

Sulfur isotopic variations were used to determine the sources of sulfur in a medium-sulfur coal (∼2 wt%S) that lacked marine influence, which is often cited as a major source of sulfur in coal. Variations in the amount and isotopic composition of the organic and pyritic sulfur among the coal-bed facies of the Upper Freeport coal bed (Middle Pennsylvanian) are attributed to differential incorporation of syngenetic and epigenetic sulfur. These variations reflect varying environmental conditions during paleopeat formation, porosity and permeability, and the availability of sulfate and iron. A large increase in the abundance and sulfur isotopic value of pyritic sulfur in the upper facies of the coal bed, in proximity to the overlying lacustrine shale, corresponds to an increase in massive and irregular forms of pyrite. This relationship is attributed to at least two stages of epigenetic pyrite incorporation. An early stage of epigenetic pyrite, moderately enriched in 34S, apparently formed during the fluvial-lacustrine period immediately following peat accumulation. A late stage of epigenetic pyrite, highly enriched in 34S, formed after compaction of the original peat as cleat- and fracture-filling pyrite; this sulfur was probably derived from bacterial reduction of dissolved sulfate in groundwater. Isotopic mass-balance calculations indicate that this late-stage epigenetic pyrite may account for up to ∼50% of the pyritic sulfur in some upper facies of the coal bed. These results suggest that most of the pyritic sulfur in the Upper Freeport coal bed may be epigenetic, incorporated either soon after peat accumulation or later during coalification.