RARE-EARTHS IN BARITES - DISTRIBUTION AND EFFECTS ON AQUEOUS PARTITIONING

A large variety of barites collected from marine and continental environments was analyzed by neutron activation for the rare-earth elements (REE) La, Ce, Sm, Eu and Dy. Relative to chondrites, all barites show a decrease of the lighter REE from La toward Eu. The abundance and distribution of rare earths in barites show a distinction of barite types. Deep-sea barites have large REE concentrations as do other authigenic deep-sea minerals and display the chondrite normalized Eu minimum, but not the negative Ce anomaly, of sea water. Other barites, mostly on land, some hydrothermal, and others of shallow marine origin, display lower total Ree concentrations. Chondrite normalized positive Eu anomalies are displayed by those varieties of reducing sedimentary and metamorphic origin. Distribution of REE in barite can be attributed both to crystallographic constraints of substitution, and to solution complexing of REE in the precipitating medium. Plots of rare earth partitioning versus effective ion size suggest that the decreasing enrichment toward Eu for all barite types is caused by crystallographic constraints due to contraction of the substituting REE ion sizes relative to the size of the host Ba ion. Solution effects on REE substitution in barite can be evaluated by writing solid solution distribution equations based on mass action of REE and Ba sulfates and the lanthanide (Ln) solution species Ln (CO3)-54), LnSO+4, LnCl+2 and LnF+2. Under normal sea water conditions, solution complexing plays a minor role. However, increased alkalinities of reducing sediments and increased brine chlorinities could cause significant complexing and deplete REE heavier than Eu. Besides Dy in barites, this could be true for aqueous precipitation of REE in general. © 1979.