Germanium-silicon fractionation in a tropical, granitic weathering environment

Germanium-silicon (Ge/Si) ratios were determined on quartz diorite bedrock, saprolite, soil, primary and secondary minerals, phytolith, soil and saprolite pore waters, and spring water and stream waters in an effort to understand Ge/Si fractionation during weathering of quartz diorite in the Rio Icacos watershed, Puerto Rico. The Ge/Si ratio of the bedrock is 2 mu mol/mol, with individual primary mineral phases ranging between 0.5 and 7 mu mol/mol. The ratios in the bulk saprolite are higher (similar to 3 mu mol/mol) than values measured in the bedrock. The major saprolite secondary mineral, kaolinite, has Ge/Si ratios ranging between 4.8 and 6.1 mu mol/mol. The high Ge/Si ratios in the saprolite are consistent with preferential incorporation of Ge during the precipitation of kaolinite. Bulk shallow soils have lower ratios (1.1-1.6 mu mol/mol) primarily due to the residual accumulation of Ge-poor quartz. Ge/Si ratios measured on saprolite and soil pore waters reflect reactions that take place during mineral transformations at discrete depths. Spring water and baseflow stream waters have the lowest Ge/Si ratios (0.27-0.47 mu mol/mol), reflecting deep initial weathering reactions resulting in the precipitation of Ge-enriched kaolinite at the saprolite-bedrock interface. Mass-balance calculations on saprolite require significant loss of Si and Al even within I m above the saprolite-bed rock interface. Higher pore water Ge/Si ratios (similar to 1.2 mu mol/mol) are consistent with partial dissolution of this Ge-enriched kaolinite. Pore water Ge/Si ratios increase up through the saprolite and into the overlying soil, but never reach the high values predicted by mass balance, perhaps reflecting the influence of phytolith recycling in the shallow soil. (C) 2009 Elsevier Ltd. All rights reserved.