Century-long record of Mo isotopic composition in sediments of a seasonally anoxic estuary (Chesapeake Bay)

A double-spike method was used to obtain Mo isotope data for sediments and waters of the seasonally anoxic Chesapeake Bay, and its primary tributary, the Susquehanna River. The dissolved Mo distribution in the estuary is non-conservative, reflecting minor Mo loss to the sediments, although removal of Mo to the sediments does not have a large influence on the isotopic composition of the water column. The δ98Mo of dissolved Mo in most of the estuary is dominated by seawater. Six samples with salinity > 15 have an average δ98Mo = + 2.17‰ (± 0.12), which agrees well with a δ98Mo value for the CASS-4 seawater standard of + 2.23‰. A single sample of Susquehanna River water has a δ98Mo of + 1.02‰, consistent with recent findings of positive δ98Mo in rivers worldwide. Susquehanna river sediments, in contrast, have δ98Mo ∼ − 0.1‰. The difference between the river water and sediment values implies that isotopic fractionation occurs within the river basin. The δ98Mo values for estuarine sediments are offset from values in the overlying water. Most samples deposited before 1925 have δ98Mo less than 0‰, similar to the Susquehanna sediments. Subsequently, there is an increase in the variability of δ98Mo, with values ranging up to + 0.8‰. The transition to increased variability coincides with the onset of authigenic Mo deposition, which was previously attributed to escalating summertime anoxia. Authigenic Mo concentrations correlate poorly with δ98Mo in core samples, suggesting that independent mechanisms influence the two parameters. Authigenic Mo concentrations may be controlled by shifting pore water H2S levels, while δ98Mo may be primarily affected by annual variations in Mn refluxing.