Sulfate enrichments in estuarine waters of North Carolina

Sulfate concentrations in the mesohaline surface waters of the Pamlico and Neuse River estuaries were enriched, relative to the conservative seawater ratio with Cl^? (0.0517 (M)), by 5 to 43% between late winter and early summer. During this period, sulfate concentrations increased to a maximum excess of 3.5 mM in the bottom waters (0.5 m deep) through intermittent periods of both very low river flow and bottom water anoxia. The calculated net sulfate production rate for this period was 18 mmol per m² per d in the bottom waters. By late summer, the excess sulfate (an average of 12 mol per m²) had been removed from the water column, presumably due to SO₄ ^?2 reduction in anoxic bottom waters and sediments. Qualitative laboratory experiments with slurries of mud exposed to excess O₂ and treated with inhibitors of cytochrome oxidase showed that it was possible to produce the excess SO₄ ^?2 under these conditions via biochemical (not chemical) oxidation of pyride that occurs within the top 5 cm of mud (ca. 100 mmol pyrite-S per g dry mud). Whether the in situ substrate for SO₄ ^?2 production was pyrite, S⁰, or S⁺², is unknown, but the predominance of aqua regia extractable pyrite-Fe and the accumulation of excess SO₄ ^?2 in slurries with insufficient other sources of oxidizable S, indicates that it may be an important substrate for biochemical production of SO₄ ^?2.