Sediment flux modeling: Simulating nitrogen, phosphorus, and silica cycles

Sediment-water exchanges of nutrients and oxygen play an important role in the biogeochemistry of shallow coastal environments. Sediments process, store, and release particulate and dissolved forms of carbon and nutrients and sediment-water solute fluxes are significant components of nutrient, carbon, and oxygen cycles. Consequently, sediment biogeochemical models of varying complexity have been developed to understand the processes regulating porewater profiles and sediment-water exchanges. We have calibrated and validated a two-layer sediment biogeochemical model (aerobic and anaerobic) that is suitable for application as a stand-alone tool or coupled to water-column biogeochemical models. We calibrated and tested a stand-alone version of the model against observations of sediment-water flux, porewater concentrations, and process rates at 12 stations in Chesapeake Bay during a 4-17 year period. The model successfully reproduced sediment-water fluxes of ammonium (NH4+,), nitrate (NO3-), phosphate (PO43-), and dissolved silica (Si(OH)(4) or DSi) for diverse chemical and physical environments. A root mean square error (RMSE)-minimizing optimization routine was used to identify best-fit values for many kinetic parameters. The resulting simulations improved the performance of the model in Chesapeake Bay and revealed (1) the need for an aerobic-layer denitrification formulation to account for NO3- reduction in this zone, (2) regional variability in denitrification that depends on oxygen levels in the overlying water, (3) a regionally-dependent solid-solute PO43- partitioning that accounts for patterns in Fe availability, and (4) a simplified model formulation for DSi, including limited sorption of DSi onto iron oxyhydroxides. This new calibration balances the need for a universal set of parameters that remain true to biogeochemical processes with site-specificity that represents differences in physical conditions. This stand-alone model can be rapidly executed on a personal computer and is well-suited to complement observational studies in a wide range of environments. (c) 2013 Elsevier Ltd. All rights reserved.