The thick regolith developed in the humid tropics represents an endmember of critical zone evolution, where shallow and deep biogeochemical cycles can be decoupled in terms of the predominant source of trace elements (atmospheric input at the surface, weathering at depth) and of the processes that control their cycling. To investigate the influence of lithology on trace element behavior and in this potential decoupling, we studied two deep (9.3 and 7.5 m), highly-leached, ridgetop regolith profiles at the Luquillo Critical Zone Observatory, Puerto Rico. These profiles have comparable internal (degree of weathering, topography) and external (vegetation, climate) characteristics, but differ in their underlying bedrock (andesitic volcaniclastic and granitic). At these two sites, we analyzed a large suite of trace elements and used the rare earth elements and yttrium (REY) as tracers of critical zone processes because they are fractionated by the chemical reactions involved in weathering and pedogenesis (e.g., sorption, dissolution, colloidal transport) and by redox fluctuations.

We found that both regolith profiles show atmospheric inputs of trace elements at the surface and evidence of bedrock dissolution at depth, as expected. We also found noticeable differences in the re-distribution of trace elements and REY within the profiles, indicative of different geochemical environments with depth and lithology. In the volcaniclastic profile, trace element and REY behavior is controlled mainly by redox-mediated, sorption/desorption reactions, whereas pH-controlled dissolution/precipitation and sorption reactions predominate in the granitic profile. The most noticeable difference between the two regolith profiles is in the long-term redox conditions, inferred from redox-sensitive elements and Ce anomaly variations, which are more variable and stratified in the volcaniclastic profile and change gradually with depth in the granitic profile. The contrasting redox conditions and the different sources of elements (dust vs. bedrock) produce a decoupling between the surface and deep geochemical environments of the volcaniclastic regolith. The difference in redox conditions between the two lithologies likely stems from the finer grain size and higher clay content of the volcaniclastic regolith.