Complexity of heterogeneous catchments poses challenges in predicting biogeochemical responses to human alterations and stochastic hydro-climatic drivers. Human interferences and climate change may have contributed to the demise of hydrologic stationarity, but our synthesis of a large body of observational data suggests that anthropogenic impacts have also resulted in the emergence of effective biogeochemical stationarity in managed catchments. Long-term monitoring data from the Mississippi-Atchafalaya River Basin (MARB) and the Baltic Sea Drainage Basin (BSDB) reveal that inter-annual variations in loads (L(T)) for total-N (TN) and total-P (TP), exported from a catchment are dominantly controlled by discharge (Q(T)) leading inevitably to temporal invariance of the annual, flow-weighted concentration, (C) over bar (f) = (L(T)/Q(T)). Emergence of this consistent pattern across diverse managed catchments is attributed to the anthropogenic legacy of accumulated nutrient sources generating memory, similar to ubiquitously present sources for geogenic constituents that also exhibit a linear L(T)-Q(T) relationship. These responses are characteristic of transport-limited systems. In contrast, in the absence of legacy sources in less-managed catchments, (C) over bar (f) values were highly variable and supply limited. We offer a theoretical explanation for the observed patterns at the event scale, and extend it to consider the stochastic nature of rainfall/flow patterns at annual scales. Our analysis suggests that: (1) expected inter-annual variations in L(T) can be robustly predicted given discharge variations arising from hydro-climatic or anthropogenic forcing, and (2) water-quality problems in receiving inland and coastal waters would persist until the accumulated storages of nutrients have been substantially depleted. The finding has notable implications on catchment management to mitigate adverse water-quality impacts, and on acceleration of global biogeochemical cycles. Citation: Basu, N. B., et al. (2010), Nutrient loads exported from managed catchments reveal emergent biogeochemical stationarity

[1] This paper presents analysis of annual water balance variability, (1) regional (betweencatchment) variability and (2) between-year (interannual) variability and the symmetry between the two. This involved analysis of the annual water balance in terms of a two-stage partitioning, first, of annual precipitation into quick flow and soil wetting and, subsequently, of the resulting soil wetting into slow flow and vaporization. The nature of this water balance partitioning is explored by completing the above analysis in 377 Model Parameter Estimation Experiment (MOPEX) catchments located across the continental United States. We fitted analytical functional relationships to the partitioning at each stage, producing expressions for the three components of quick flow, slow flow, and vaporization. They indicate that the heterogeneity of water balance partitioning among the MOPEX catchments is underlain by a universal relationship that is transferable regionally. Key nondimensional similarity parameters are identified that serve to connect this invariant regional relationship to site-specific response characteristics. These nondimensional formulations are extended to derive analytical expressions for several common metrics of annual water balance. The ability of the functional theory to predict regional patterns of mean annual water balance and interannual variability in individual catchments is assessed. Our analyses show a close symmetry between spatial (regional) variability of mean annual water balances and general trends of temporal (interannual) variability. The suggested functional theory can thus be the basis for data-based assessments of hydrologic similarity and used to assist with predictions of the effects of long-term climate variability and change, through providing a theoretical framework for ''space for time'' substitutions.

Abstract. The flow duration curve (FDC) is a classical method used to graphically represent the relationship between the frequency and magnitude of streamflow. In this sense it represents a compact signature of temporal runoff variability that can also be used to diagnose catchment rainfall-runoff responses, including similarity and differences between catchments. This paper is aimed at extracting regional patterns of the FDCs from observed daily flow data and elucidating the physical controls underlying these patterns, as a way to aid towards their regionalization and predictions in ungauged basins. The FDCs of total runoff (TFDC) using multi-decadal streamflow records for 197 catchments across the continental United States are separated into the FDCs of two runoff components, i.e., fast flow (FFDC) and slow flow (SFDC). In order to compactly display these regional patterns, the 3-parameter mixed gamma distribution is employed to characterize the shapes of the normalized FDCs (i.e., TFDC, FFDC and SFDC) over the entire data record. This is repeated to also characterize the between-year variability of "annual" FDCs for 8 representative catchments chosen across a climate gradient. Results show that the mixed gamma distribution can adequately capture the shapes of the FDCs and their variation between catchments and also between years. Comparison between the between-catchment and between-year variability of the FDCs revealed significant space-time symmetry. Possible relationships between the parameters of the fitted mixed gamma distribution and catchment climatic and physiographic characteristics are explored in order to decipher and point to the underlying physical controls. The baseflow index (a surrogate for the collective impact of geology, soils, topography and vegetation, as well as climate) is found to be the dominant control on the shapes of the normalized TFDC and SFDC, whereas the product of maximum daily precipitation and the fraction of non-rainy days was found to control the shape of the FFDC. These relationships, arising from the separation of total runoff into its two components, provide a potential physical basis for regionalization of FDCs, as well as providing a conceptual framework for developing deeper process-based understanding of the FDCs.

Abstract. Predictions of hydrological responses in ungauged catchments can benefit from a classification scheme that can organize and pool together catchments that exhibit a level of hydrologic similarity, especially similarity in some key variable or signature of interest. Since catchments are complex systems with a level of self-organization arising from co-evolution of climate and landscape properties, including vegetation, there is much to be gained from developing a classification system based on a comparative study of a population of catchments across climatic and landscape gradients. The focus of this paper is on climate seasonality and seasonal runoff regime, as characterized by the ensemble mean of within-year variation of climate and runoff. The work on regime behavior is part of an overall study of the physical controls on regional patterns of flow duration curves (FDCs), motivated by the fact that regime behavior leaves a major imprint upon the shape of FDCs, especially the slope of the FDCs. As an exercise in comparative hydrology, the paper seeks to assess the regime behavior of 428 catchments from the MOPEX database simultaneously, classifying and regionalizing them into homogeneous or hydrologically similar groups. A decision tree is developed on the basis of a metric chosen to characterize similarity of regime behavior, using a variant of the Iterative Dichotomiser 3 (ID3) algorithm to form a classification tree and associated catchment classes. In this way, several classes of catchments are distinguished, in which the connection between the five catchments' regime behavior and climate and catchment properties becomes clearer. Only four similarity indices are entered into the algorithm, all of which are obtained from smoothed daily regime curves of climatic variables and runoff. Results demonstrate that climate seasonality plays the most significant role in the classification of US catchments, with rainfall timing and climatic aridity index playing somewhat secondary roles in the organization of the catchments. In spite of the tremendous heterogeneity of climate, topography, and runoff behavior across the continental United States, 331 of the 428 catchments studied are seen to fall into only six dominant classes.

Abstract. The goal of this paper is to explore the process controls underpinning regional patterns of variations of streamflow regime behavior, i.e., the mean seasonal variation of streamflow within the year, across the continental United States. The ultimate motivation is to use the resulting process understanding to generate insights into the physical controls of another signature of streamflow variability, namely the flow duration curve (FDC). The construction of the FDC removes the time dependence of flows. Thus in order to better understand the physical controls in regions that exhibit strong seasonal dependence, the regime curve (RC), which is closely connected to the FDC, is studied in this paper and later linked back to the FDC. To achieve these aims a top-down modeling approach is adopted; we start with a simple two-stage bucket model, which is systematically enhanced through addition of new processes on the basis of model performance assessment in relation to observations, using rainfall-runoff data from 197 United States catchments belonging to the MOPEX dataset. Exploration of dominant processes and the determination of required model complexity are carried out through model-based sensitivity analyses, guided by a performance metric. Results indicated systematic regional trends in dominant processes: snowmelt was a key process control in cold mountainous catchments in the north and north-west, whereas snowmelt and vegetation cover dynamics were key controls in the north-east; seasonal vegetation cover dynamics (phenology and interception) were important along the Appalachian mountain range in the east. A simple two-bucket model (with no other additions) was found to be adequate in warm humid catchments along the west coast and in the south-east, with both regions exhibiting strong seasonality, whereas much more complex models are needed in the dry south and southwest. Agricultural catchments in the mid-west were found to be difficult to predict with the use of simple lumped models, due to the strong influence of human activities. Overall, these process controls arose from general east-west (seasonality) and north-south (aridity, temperature) trends in climate (with some exceptions), compounded by complex dynamics of vegetation cover and to a less extent by landscape factors (soils, geology and topography).