Cycling of dissolved rare earth elements in Chesapeake Bay

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Abstract
The measurement of dissolved rare earth elements (REE) in the surface waters, water column of anoxic basins, and pore waters in Chesapeake Bay has provided new insights to the biogeochemistry and estuarine chemistry of REE. All dissolved REE from the riverine source show large‐scale removal in the lower salinity zone (0‐10‰). The shale‐normalized pattern of dissolved Susquehanna River water is opposite in form to that of surface sediments in the Bay. The former is enriched in heavy REE (HREE) while the latter are enriched in light REE (LREE). Neither component has a flat pattern normally assumed for river‐ transported REE to the ocean. The dissolved LREE (i.e., La, Ce, Nd, Sm, and Eu) are enriched 3 to 9 times) in the oxygen‐depleted deep waters over their concentrations in the oxic surface waters. In contrast, HREE (Er, Yb, and Lu) are slightly depleted. All REE concentrations in the two surface (0‐2 cm) pore waters are greatly enriched (8‐17 times; 43 times for Ce) relative to oxygen‐depleted bottom waters and have relative abundances opposite to those of their sediments. While Ce has a positive anomaly in the pore waters, negative anomalies exist in the oxygen‐depleted bottom waters. The REE are participating in a set of complex biogeochemical cycles within the water column and surface sediments. Fractionation of REE during these cycles leads to the preferential enrichment of LREE in the seasonally oxygen‐depleted bottom waters. It is proposed that this fractionation is coupled to redox cycles of Mn and Fe and the interaction of dissolved REE with suspended particles and surficial sediments.