Exposure times rather than residence times control redox transformation efficiencies in riparian wetlands

The concept of Damkohler numbers have been extensively used in the discipline of chemical engineering and lately increasingly found its application into environmental science in order to describe the integrated behavior of hydrological systems with respect to their physical transport and biogeochemical transformation capabilities. Defining characteristic time scales of transport and reaction, as part of the Damkohler concept, however is not trivial especially for non-well mixed systems like catchments where physically controlled transport and biogeochemical moderated reactions can be highly variable among individual flow paths. Often, system specific residence times alone are not useful to describe the time scales of transport in the Damkohler concept, because it neglects that degradation of redox-sensitive compounds depend on dynamically changing and non-uniformly distributed hydro-biogeochemical boundary conditions that either facilitate or suppress biogeochemical reactions. In this study an approach is presented that highlights the importance to specifically distinguish between residence and exposure times if system specific transformation efficiencies are evaluated. We investigate the inter-relationship between residence and exposure time distributions for different biogeochemical processes in a virtual wetland environment that is exposed to different hydrological conditions. The relationship between exposure and residence times is mathematically described by a composition matrix that linearly relates the two identities to each other. Composition matrices for different hydrological conditions are analyzed by using the singular value decomposition technique. Results show that especially the type of couplings between the surface and subsurface flow domain control how exposure and residence times are related to each other in the wetland system and that timescales of residence and exposure typically differ by orders of magnitude. Finally, results also indicate that the assessment of system specific transformation efficiencies can be very error-prone if residence instead of exposure times are being used to derive system specific Damkohler numbers. (C) 2016 Elsevier B.V. All rights reserved.