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Summary: The aim of this study was, within a sensitivity analysis framework, to determine if additional model complexity gives a better capability to model the hydrology and nitrogen dynamics of a small Mediterranean forested catchment or if the additional parameters cause over-fitting. Three nitrogen-models of varying hydrological complexity were considered. For each model, general sensitivity analysis (GSA) and Generalized Likelihood Uncertainty Estimation (GLUE) were applied, each based on 100,000 Monte Carlo simulations. The results highlighted the most complex structure as the most appropriate, providing the best representation of the non-linear patterns observed in the flow and streamwater nitrate concentrations between 1999 and 2002. Its 5% and 95% GLUE bounds, obtained considering a multi-objective approach, provide the narrowest band for streamwater nitrogen, which suggests increased model robustness, though all models exhibit periods of inconsistent good and poor fits between simulated outcomes and observed data. The results confirm the importance of the riparian zone in controlling the short-term (daily) streamwater nitrogen dynamics in this catchment but not the overall flux of nitrogen from the catchment. It was also shown that as the complexity of a hydrological model increases over-parameterisation occurs, but the converse is true for a water quality model where additional process representation leads to additional acceptable model simulations. Water quality data help constrain the hydrological representation in process-based models. Increased complexity was justifiable for modelling river-system hydrochemistry. Increased complexity was justifiable for modelling river-system hydrochemistry. [Copyright &y& Elsevier]

The Integrated Catchment Model of Nitrogen (INCA-N) was applied to the River Lambourn, a Chalk river-system in southern England. The model''s abilities to simulate the long-term trend and seasonal patterns in observed stream water nitrate concentrations from 1920 to 2003 were tested. This is the first time a semi-distributed, daily time-step model has been applied to simulate such a long time period and then used to calculate detailed catchment nutrient budgets which span the conversion of pasture to arable during the late 1930s and 1940s. Thus, this work goes beyond source apportionment and looks to demonstrate how such simulations can be used to assess the state of the catchment and develop an understanding of system behaviour. The mass-balance results from 1921, 1922, 1991, 2001 and 2002 are presented and those for 1991 are compared to other modelled and literature values of loads associated with nitrogen soil processes and export. The variations highlighted the problem of comparing modelled fluxes with point measurements but proved useful for identifying the most poorly understood inputs and processes thereby providing an assessment of input data and model structural uncertainty. The modelled terrestrial and instream mass-balances also highlight the importance of the hydrological conditions in pollutant transport. Between 1922 and 2002, increased inputs of nitrogen from fertiliser, livestock and deposition have altered the nitrogen balance with a shift from possible reduction in soil fertility but little environmental impact in 1922, to a situation of nitrogen accumulation in the soil, groundwater and instream biota in 2002. In 1922 and 2002 it was estimated that approximately 2 and 18 kg N ha−1 yr−1 respectively were exported from the land to the stream. The utility of the approach and further considerations for the best use of models are discussed. [Copyright &y& Elsevier]

Abstract: This paper describes the results and conclusions of the INCA (Integrated Nitrogen Model for European CAtchments) project and sets the findings in the context of the ELOISE (European Land-Ocean Interaction Studies) programme. The INCA project was concerned with the development of a generic model of the major factors and processes controlling nitrogen dynamics in European river systems, thereby providing a tool (a) to aid the scientific understanding of nitrogen transport and retention in catchments and (b) for river-basin management and policy-making. The findings of the study highlight the heterogeneity of the factors and processes controlling nitrogen dynamics in freshwater systems. Nonetheless, the INCA model was able to simulate the in-stream nitrogen concentrations and fluxes observed at annual and seasonal timescales in Arctic, Continental and Maritime-Temperate regimes. This result suggests that the data requirements and structural complexity of the INCA model are appropriate to simulate nitrogen fluxes across a wide range of European freshwater environments. This is a major requirement for the production of coupled river-estuary-coastal shelf models for the management of our aquatic environment. With regard to river-basin management, to achieve an efficient reduction in nutrient fluxes from the land to the estuarine and coastal zone, the model simulations suggest that management options must be adaptable to the prevailing environmental and socio-economic factors in individual catchments: ‘Blanket approaches’ to environmental policy appear too simple. [Copyright &y& Elsevier]

Abstract: There are now considerable expectations that semi-distributed models are useful tools for supporting catchment water quality management. However, insufficient attention has been given to evaluating the uncertainties inherent to this type of model, especially those associated with the spatial disaggregation of the catchment. The Integrated Nitrogen in Catchments model (INCA) is subjected to an extensive regionalised sensitivity analysis in application to the River Kennet, part of the groundwater-dominated upper Thames catchment, UK The main results are: (1) model output was generally insensitive to land-phase parameters, very sensitive to groundwater parameters, including initial conditions, and significantly sensitive to in-river parameters; (2) INCA was able to produce good fits simultaneously to the available flow, nitrate and ammonium in-river data sets; (3) representing parameters as heterogeneous over the catchment (206 calibrated parameters) rather than homogeneous (24 calibrated parameters) produced a significant improvement in fit to nitrate but no significant improvement to flow and caused a deterioration in ammonium performance; (4) the analysis indicated that calibrating the flow-related parameters first, then calibrating the remaining parameters (as opposed to calibrating all parameters together) was not a sensible strategy in this case; (5) even the parameters to which the model output was most sensitive suffered from high uncertainty due to spatial inconsistencies in the estimated optimum values, parameter equifinality and the sampling error associated with the calibration method; (6) soil and groundwater nutrient and flow data are needed to reduce uncertainty in initial conditions, residence times and nitrogen transformation parameters, and long-term historic data are needed so that key responses to changes in land-use management can be assimilated. The results indicate the general difficulty of reconciling the questions which catchment nutrient models are expected to answer with typically limited data sets and limited knowledge about suitable model structures. The results demonstrate the importance of analysing semi-distributed model uncertainties prior to model application, and illustrate the value and limitations of using Monte Carlo-based methods for doing so. [Copyright &y& Elsevier]

Reactive nitrogen (N) and phosphorus (P) inputs to surface waters modify aquatic environments, affect public health and recreation. Source controls dominate eutrophication management, whilst biological regulation of nutrients is largely neglected, although aquatic microbial organisms have huge potential to process nutrients. The stoichiometric ratio of organic carbon (OC) to N to P atoms should modulate heterotrophic pathways of aquatic nutrient processing, as high OC availability favours aquatic microbial processing. Heterotrophic microbial processing removes N by denitrification and captures N and P as organically-complexed, less eutrophying forms. With a global data synthesis, we show that the atomic ratios of bioavailable dissolved OC to either N or P in rivers with urban and agricultural land use are often distant from a “microbial optimum”. This OC-deficiency relative to high availabilities of N and P likely overwhelms within-river heterotrophic processing. We propose that the capability of streams and rivers to retain N and P may be improved by active stoichiometric rebalancing. Although autotrophic OC production contributes to heterotrophic rates substantial control on nutrient processing from allochthonous OC is documented for N and an emerging field for P. Hence, rebalancing should be done by reconnecting appropriate OC sources such as wetlands and riparian forests that have become disconnected from rivers concurrent with agriculture and urbanisation. However, key knowledge gaps require research prior to the safe implementation of this approach in management: (i) to evaluate system responses to catchment inputs of dissolved OC forms and amounts relative to internal production of autotrophic dissolved OC and aquatic and terrestrial particulate OC and (ii) evaluate risk factors in anoxia-mediated P desorption with elevated OC scenarios. Still, we find stoichiometric rebalancing through reconnecting landscape beneficial OC sources has considerable potential for river management to alleviate eutrophication, improve water quality and aquatic ecosystem health, if augmenting nutrient source control. [ABSTRACT FROM AUTHOR]