Imbalances in Dissolved Elemental Export Fluxes Disclose “Hidden” Critical Zone Compartments

In streams, short-term element-specific solute fluxes are often not balanced with long-term chemical weathering fluxes determined in the residual solids from fractional element loss and denudation rate. The ratio of both estimates—the “Dissolved Export Efficiency” (DEE)—is frequently <1, indicating deficits in the stream dissolved load. To explore the cause of the stream deficits, we performed a daily water sampling campaign for one year in a forested headwater watershed in Southern Germany. We sampled surface runoff, above-canopy and below-canopy precipitation, subsurface flow from the organic soil layer, upper, and deep mineral soil, and groundwater. Regolith samples were obtained from a drill core and revealed the weathering front to lie between 7 and 15 m depth. We found a DEE < 1 for K, Si, Al, Fe. These elements are characterized by shallow slopes in C-Q relationships, and the imbalances were found to originate in the deep saprolite. Their export pathway potentially includes “hidden” Critical Zone compartments or fluxes, presumably unsampled colloids that are exported preferentially during rare flushing events with stochastic temporal distribution. The DEE of nutritive elements like Ca, Mg, and P is also <1. These elements are characterized by steeper C-Q slopes, and their imbalance can be explained by deep nutrient uptake followed by nutrient retainment in re-growing forest biomass or export in plant debris. The collective evidence for these imbalances, including previous evidence from metal stable isotopes, suggests that the deep Critical Zone represents the location for chemical or biogenic retention and release of solutes.