Rare earth elements (REE) were determined in fine, medium and coarse crystalline replacement dolomites, and for saddle dolomite cements from the Middle Devonian Presqu'ile barrier from Pine Point and the subsurface of the Northwest Territories and north-eastern British Columbia. REE patterns of the fine crystalline dolomite are similar to those of Middle Devonian limestones from the Presqu'ile barrier. Fine crystalline dolomite occurs in the back-barrier facies and may represent penecontemporaneous dolomitization at, or just below, the sea floor. Medium crystalline dolomite is widespread in the lower southern and lower central barrier. Medium crystalline dolomite is slightly depleted in heavy REE compared with Devonian marine limestones and fine crystalline dolomite, and has negative Ce and Eu anomalies. Medium crystalline dolomites replaced pre-existing limestones or were recrystallized from earlier fine crystalline dolomites. During these processes, the REE patterns of their precursors were modified. Late stage, coarse crystalline replacement dolomite and saddle dolomite cements occur together in the upper barrier and have similar geochemical signatures. Coarse crystalline dolomites have negative Eu anomalies, and those from the Pine Point area also have positive La anomalies. Saddle dolomites are enriched in light REE and have positive La anomalies. The REE patterns of coarse crystalline dolomite and saddle dolomite differ from those of marine limestones and fine and medium crystalline dolomites, suggesting that different diagenetic fluids were responsible for these later dolomites.
Although massive dolomitization requires relatively large volumes of fluids in order to provide the necessary amounts of Mg2-. dolomitization and subsequent recrystallization may not necessarily modify the REE signatures of the precursor limestones because of the low concentrations of REE in most natural fluids. Thus, relative fluid-rock ratios during diagenesis may be estimated from REE patterns in the diagenetic and precursor minerals. Fine crystalline dolomites retain the REE patterns of their limestone precursors. In the medium and coarse crystalline dolomites the precursor REE patterns were apparently altered by large volumes of fluids involved during dolomitization. This study suggests that REE compositions of dolomites and their limestone precursors may provide important information about the relative amounts of fluids involved during diagenetic processes, such as dolomitization.