The rare earth elements in rivers, estuaries, and coastal seas and their significance to the composition of ocean waters

The biogeochemistry of manganese and iron reduction in marine sediments

Much attention has been paid, in recent years, to the potential application of the Ce anomaly, measured in various marine phases, as a paleoceanographic indicator of widespread marine anoxia. In this paper we present and discuss results from recent studies of present-day rare earth element (REE) distributions (and hence Ce anomaly distributions) in the marine environment which are particularly pertinent to paleoceanography. Subsequently, we review and discuss the validity of the recent literature in which Ce anomalies have been employed as paleoredox indicators.

Application of the Ce anomaly as a paleoredox indicator: The ground rules

Laboratory experiments were carried out to determine how pH, colloids and salinity control the fractionation of rare earth elements (REEs) in river and estuarine waters. By using natural waters as the reaction media (river water from the Connecticut, Hudson and Mississippi Rivers) geochemical reactions can be studied in isolation from the large temporal and spatial variability inherent in river and estuarine chemistry. Experiments, field studies and chemical models form a consistent picture whereby REE fractionation is controlled by surface/solution reactions. The concentration and fractionation of REEs dissolved in river waters are highly pH dependent. Higher pH results in lower concentrations and more fractionated composition relative to the crustal abundance. With increasing pH the order of REE adsorption onto river particle surfaces is LREEs > MREEs > HREEs. With decreasing pH, REEs are released from surfaces in the same order. Within the dissolved ( MREEs > LREEs, is most pronounced in the solution pool, defined here as MREEs > HREEs. While the large scale removal of dissolved river REEs in estuaries is well established, the release of dissolved REEs off river particles is a less studied process. Laboratory experiments show that there is both release and fractionation of REEs when river particles are leached with seawater. The order of sea water-induced release of dissolved REE(III) (LREEs > MREEs > HREEs) from Connecticut River particles is the same as that associated with lowering the pH and the same as that associated with colloidal particles. River waters, stripped of their colloidal particles by coagulation in estuaries, have highly evolved REE composition. That is, the solution pool of REEs in river waters are strongly HREE-enriched and are fractionated to the same extent as that of Atlantic surface seawater. This strengthens the conclusions of previous studies that the evolved REE composition of sea water is coupled to chemical weathering on the continents and reactions in estuaries. Moreover, the release of dissolved Nd from river particles to sea water may help to reconcile the incompatibility between the long oceanic residence times of Nd (7100 yr) and the inter-ocean variations of the Nd isotopic composition of sea water. Using new data on dissolved and particle phases of the Amazon and Mississippi Rivers, a comparison of field and laboratory experiments highlights key features of REE fractionation in major river systems. The dissolved pool of both rivers is highly fractionated (HREE enriched) with respect to the REE composition of their suspended particles. In addition, the dissolved pool of the Mississippi River has a large negative Ce-anomaly suggesting in-situ oxidation of Ce(III). One intriguing feature is the well developed maximum in the middle REE sector of the shale normalized patterns for the dissolved pool of Amazon River water. This feature might reflect competition between surface adsorption and solution complexation with carbonate and phosphate anions.

The Aquatic Chemistry of Rare Earth Elements in Rivers and Estuaries

Rare Earth Element and yttrium compositions of Archean and Paleoproterozoic Fe formations revisited: New perspectives on the significance and mechanisms of deposition

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.

H. Elderfield

Papers

Cycling of dissolved rare earth elements in Chesapeake Bay